CN107961797B - Regeneration method of amination catalyst for preparing polyether amine by hydroamination of polyether polyol - Google Patents

Regeneration method of amination catalyst for preparing polyether amine by hydroamination of polyether polyol Download PDF

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CN107961797B
CN107961797B CN201711171853.1A CN201711171853A CN107961797B CN 107961797 B CN107961797 B CN 107961797B CN 201711171853 A CN201711171853 A CN 201711171853A CN 107961797 B CN107961797 B CN 107961797B
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catalyst
amination catalyst
regeneration
amination
acid solution
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CN107961797A (en
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任树杰
张聪颖
李鑫
刘振国
唐磊
吴健
姜庆梅
曹善健
黎源
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Wanhua Chemical Group Co Ltd
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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
    • B01J38/10—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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J38/02—Heat treatment
    • 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
    • B01J38/16—Oxidation gas comprising essentially steam and oxygen
    • 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
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/328—Polymers modified by chemical after-treatment with inorganic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The invention discloses a regeneration method of an amination catalyst for preparing polyether amine by hydroamination of polyether polyol, which comprises the following steps: (A) adding the inactivated amination catalyst into an organic acid solution, heating and refluxing, filtering, washing and drying; (B) carrying out charcoal burning regeneration on the amination catalyst obtained by washing and drying treatment in the presence of hydrogen peroxide to obtain a roasted and regenerated amination catalyst; (C) and (3) reducing the calcined and regenerated amination catalyst by using hydrogen to obtain the reductive and regenerated amination catalyst. The regeneration treatment method solves the problems of copper sintering and Ni of active components of the catalyst due to coking and even carbon deposition0A method for regenerating deactivated amination catalysts caused by aggregation of crystalline phases. The regeneration treatment method is mainly applied to the regeneration treatment process of the amination catalyst for preparing polyether amine by hydroamination of polyether polyol.

Description

Regeneration method of amination catalyst for preparing polyether amine by hydroamination of polyether polyol
Technical Field
The invention relates to a regeneration method of an amination catalyst for preparing polyether amine by hydroamination of polyether polyol, in particular to a method for regenerating a catalyst, which is used for preparing polyether amine by hydroamination reaction deactivation of polyether polyol by using a catalyst which is composed of more than two metals selected from Ni, Co, Cu and Pd as active components, and more than one metal selected from Zr, Cr, Mo, Fe, Zn, Sn, Ce, Mg, Mn, La, Hf, Sr, V, Mn, W, Pb, Pt, Ag, Rh, Ru, Bi, Nd, Sb and Be auxiliaries or oxides thereof, and especially taking alumina as a carrier.
Background
The Polyether amine is also called Amino-Terminated Polyether (ATPE for short) which is a polyoxyalkylene compound with a Polyether backbone and Amino-Terminated end. These amine-terminated polyethers mostly use polyethers (polyethylene glycol, polyoxypropylene ether, etc.) as reaction raw materials, and convert the terminal hydroxyl groups of polyether polyols into corresponding amine groups or amino groups (the terminal groups are usually primary, secondary or polyamine groups containing active hydrogen) by different chemical treatment methods. Due to the reactivity of the tail amino group or the amine group of the polyether framework, the polyether framework can react with various reactive groups, such as epoxy groups, isocyanate groups and the like; in addition, due to the existence of ether bonds in the polyether chain, the polyether amine is easy to dissolve in various organic matters, so that the application range of the polyether amine in the industrial field is greatly widened. Therefore, polyetheramines are widely used in the fields of epoxy resin curing agents, polyurethane (polyurea) industry, gasoline detergent dispersants, and the like, because of their excellent properties.
The synthesis method of the polyether amine mainly comprises a reductive amination method, a leaving group method and a polyether nitrile reduction method. The reductive amination method is also called as hydroamination method, the process route is most advanced, and the produced product has the most stable quality and better meets the requirement of environmental protection, so the reductive amination method becomes the main industrial production method of the polyether amine at home and abroad. The key to the production process is the selection and preparation of the catalyst. Catalysts suitable for reductive amination contain metals such as Ni, Co and Cu as the active components, sometimes referred to as hydrogenation/dehydrogenation catalysts because they are active in both types of reactions. Other elements of the periodic table are also frequently introduced into the catalyst to provide the catalyst with optimal activity or selectivity.
US4014933 discloses an alumina or silica supported Co-Ni-Cu catalyst and a process for the amination of polypropylene glycols. The catalyst comprises 10% of Co, 10% of Ni, 4% of Cu and 0.4% of phosphoric acid, and the balance of Al2O3. The catalyst is suitable for amination reaction of polyether polyol with molecular weight greater than 1400.
US4152353 and US4153581 disclose an alumina supported catalyst of Ni, Cu and one or two metals selected from Fe and Zn promoters comprising 30% Ni (or 30% Co), 63% Cu and 7% Fe and/or Zn, the remainder being Al2O3。
US4209424 discloses an alumina supported transition metal amination catalyst and its use in the amination of polyether polyols, the catalyst comprising at least one or two of Ni, Co and Cu, wherein the metal content is 30-70%, the remainder being Al2O3。
US4973761 discloses an alumina supported Ni, Co and Cu amination catalyst and its use for the amination of polytetrahydrofuran ether glycols. The catalyst is suitable for the amination of polyether polyols with molecular weights of 640-4000.
US5003107 discloses an alumina supported Ni, Co, Cr, Mo amination catalyst and its use in the amination of polyoxytetramethylene glycol. The catalyst comprises 70-75% of Ni, 20-25% of Cu, 0.5-5% of Cr and 1-5% of Mo, and the balance of Al2O3. When a continuous tubular reactor is used, the raw material conversion rate reaches 91-96% and the product selectivity reaches 92-97% in the process of ammoniating polytetrahydrofuran polyether with the molecular weight of 1000 and 2000. The catalyst does not involve polyethers having a molecular weight of less than 500Amination of the polyol.
CN102781571 discloses an Al2O3A preparation method of a supported catalyst. Based on the total amount of the catalyst, the Ni content is 16-22%, the Co content is 17-21%, the Cu content is 9-11%, the Sn content is 0.5-2%, the yttrium, lanthanum, cerium and/or hafnium content is 0.5-2%, and the rest is Al2O3。
CN106669731A discloses Al2O3A preparation method of a supported catalyst. Based on the total amount of the catalyst, the active component Ni content is 5-30wt%, the Cu content is 5-25%, the Pd content is 0.3-2.0%, the auxiliary agents V, Cr, Mn, Fe, Co, Zn, Mo, W, Sn, Pb, Bi, La, Ce, Nd and/or Sm content is 0-5%, and the balance is Al2O3。
Problems common to the above amination catalysts: the activity of the catalyst decreases with the time of use during use, i.e. the catalyst deactivates. The factors causing the deactivation of the catalyst are many, and can be attributed to the influence of impurities in the raw materials, the influence of reaction conditions, and the deactivation caused by the change of catalyst components and structures in the reaction process, such as various factors of poisoning, blockage, sintering, thermal deactivation and the like. However, the reasons for the deactivation of the amination catalysts used for the synthesis of polyetheramines can be summarized in the following areas:
(1) polyether polyol used as a raw material for synthesizing polyether amine is a mixture consisting of polyethers with different chain lengths and molecular weights, and the activity of the polyether is weakened along with the increase of a carbon chain. Under the same reaction, along with the hydroamination reaction of the polyether part with lower activity, the polyether part with higher activity is easy to generate a ring-closing reaction to generate a dimethyl morpholine by-product, and the dimethyl morpholine by-product is a nitrogen heterocyclic ring strong-basicity substance which is easy to adsorb and difficult to desorb at an acid site of the catalyst, and is easy to further react to generate a basic coking compound and even carbon deposition, so that a catalyst pore channel is blocked, and an active site of the catalyst is covered, so that the catalyst is gradually inactivated.
(2) During the amination reaction, the active component copper reacts with ammonia in the raw material to convert into inactive copper nitride (Cu)3N) covering the surface of the catalyst to block the catalyst pore channels,covering the catalyst active sites. Meanwhile, since copper is a low melting point metal, when the temperature reaches 30% of its melting point, sintering easily occurs, so that the particle size increases, the surface area decreases, and the catalyst is deactivated.
(3) In the amination reaction, the active component Ni0With carrier Al2O3Form NiAl therebetween2O4And an active component Ni0The aggregation of the crystalline phase reduces the number of active sites on the catalyst surface, resulting in a gradual deactivation of the catalyst.
In order to solve the problem of deactivation of the amination catalyst, researchers at home and abroad research the regeneration of the amination catalyst. CN1165712A discloses a method for regenerating a catalyst consisting of an alumina carrier and two or more metals selected from Ni, Cu, Cr, Ti and Re or oxides thereof after the deactivation of amination reaction, wherein the activity of the deactivated catalyst can be recovered by roasting or/and washing or/and soaking in an impregnation solution. In the patent, a large amount of organic solvent is adopted for washing the catalyst in the washing process, so that the problems of solvent waste and solvent recovery cost exist; in the dipping process, concentrated nitric acid solution with acid concentration of 15-30% is used for dipping the catalyst, so that the problems of destroying the structure of the alumina carrier and dissolving active components exist; in the roasting process, air or nitrogen or mixed gas of air and nitrogen in any proportion is adopted for high-temperature roasting, so that the problems of rehydration of the carrier alumina can be solved, and the dispersion degree of the active components can be reduced and the active components can be sintered.
Disclosure of Invention
It is an object of the present invention to provide a process for regenerating amination catalysts, in particular due to coking or even carbon deposition, sintering of the active components copper of the catalyst and Ni0A method for regenerating deactivated amination catalysts caused by aggregation of crystalline phases.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a process for regenerating an amination catalyst used in the hydroamination of polyether polyols to produce polyether amines, which process comprises:
(A) adding the inactivated amination catalyst into an organic acid solution, heating and refluxing, filtering, washing (preferably washing to be neutral), and drying;
(B) carrying out charcoal burning regeneration on the amination catalyst obtained by washing and drying treatment in the presence of hydrogen peroxide to obtain a roasted and regenerated amination catalyst;
(C) and (3) reducing the calcined and regenerated amination catalyst by using hydrogen to obtain the reductive and regenerated amination catalyst.
The amination catalyst can Be any amination catalyst commonly used in the field, and further comprises alumina as a carrier, more than two of Ni, Co, Cu and Pd as active components, and more than one metal or oxide of Zr, Cr, Mo, Fe, Zn, Sn, Ce, Mg, Mn, La, Hf, Sr, V, Mn, W, Pb, Pt, Ag, Rh, Ru, Bi, Nd, Sb and Be auxiliary agents as auxiliary agents. For example, based on the total amount of the catalyst, the active component Ni is 5 wt% to 30wt%, Cu is 5 wt% to 25 wt%, Pd is 0.3 wt% to 2.0 wt%, Co is 5 wt% to 25 wt%, the auxiliary agent is 0.5 wt% to 5 wt%, and the balance is Al2O3。
Preferably, the concentration of the organic acid solution is 5 to 30wt%, and the organic acid solution is selected from one or more of a formic acid solution, an acetic acid solution, a tartaric acid solution, an oxalic acid solution and a carbonic acid solution, preferably an acetic acid solution, wherein the concentration of the acetic acid solution is preferably 10 to 20 wt%. Solid-liquid volume ratio (volume ratio of deactivated amination catalyst to organic acid solution) 1: 1-20, preferably 1: 5-10. The heating reflux time is 1-10h, preferably 3-8 h.
In the step (B), the amination catalyst obtained by washing and drying treatment is subjected to solid-liquid volume ratio of 1: introducing 3-30wt% hydrogen peroxide solution 10-50 to regenerate charcoal, wherein the calcination time is 1-15h, preferably 5-10 h.
In the step (C), the reaction is carried out at the temperature of 100 ℃ and 400 ℃ by using a solvent with the volume ratio of 1: reducing the mixed gas of hydrogen and nitrogen of 1-100 parts for 1-20 hours, and cooling to ambient temperature.
In one embodiment, a regeneration process for an amination catalyst used in the hydroamination of polyether polyols to produce polyether amines comprises:
a washing step: according to the solid-liquid volume ratio of 1: 1-20, adding the inactivated amination catalyst into an organic acid solution with the concentration of 5-30wt%, heating and refluxing for 1-10h, filtering, washing to be neutral, and drying;
and (3) roasting: at normal pressure, placing the amination catalyst obtained by washing and drying treatment in a fixed bed reactor, heating to 200-600 ℃, wherein the heating rate is 1-10 ℃/min, and the solid-liquid volume ratio is 1: introducing 3-30wt% hydrogen peroxide solution 10-50 for charcoal-burning regeneration for 1-15 hr until no CO is detected in tail gas2Generating and cooling to obtain an amination catalyst after roasting and regeneration;
a reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 100-400 ℃, the heating rate is 0.1-2 ℃/min, and the volume ratio is 1: 1-100 of hydrogen/nitrogen mixed gas is fully reduced for 1-20 hours, and the temperature is reduced, thus obtaining the amination catalyst after reduction and regeneration.
The concentration of the hydrogen peroxide solution in the calcination step is preferably 10 to 20% by weight, more preferably 12 to 16% by weight. The solid-liquid volume ratio is preferably 1: 20-35. The roasting temperature is preferably 300-450 ℃, the heating rate is preferably 3-5 ℃/min, and the roasting time is preferably 5-10 h.
The reduction temperature is preferably 200-300 ℃, the heating rate is preferably 0.5-1 ℃/min, the reduction time is preferably 5-10h, and the volume ratio of hydrogen to nitrogen is preferably 1: 10-80, more preferably 1: 40-60.
The regeneration method of the present invention must be implemented in sequence according to the above operation processes, and any one-step operation or any change of the operation sequence thereof cannot achieve the optimal regeneration effect. The regeneration process of the present invention may be carried out at any time during the use of the amination catalyst, in particular after 1000 hours of use of the catalyst.
The invention has the beneficial effects that:
(1) the organic acid is adopted for coke dissolving regeneration, most of alkaline coking compounds blocking the catalyst pore channels are dissolved, the active site part covering the surface of the catalyst is exposed, and the activity of the catalyst is improved. Meanwhile, compared with inorganic acid, the organic acid is relatively weak in acidity, and the problems of destroying the carrier structure and dissolving the active component do not exist.
(2) The coked amination catalyst is roasted and regenerated by adopting hydrogen peroxide, and oxygen and water vapor generated by in-situ decomposition of the hydrogen peroxide at high temperature are generated, so that on one hand, coke which is not dissolved and washed away can be completely burnt out by carrying out carbon burning regeneration in the oxygen-water vapor atmosphere, active sites covered on the surface of the catalyst are fully exposed, and the catalytic performance of the deactivated catalyst caused by blocking catalyst pore channels and covering the active sites of the catalyst is completely recovered. On the other hand, oxidation of oxygen generated by pyrolysis of hydrogen peroxide enables the sintered active component copper to form a thin oxide layer and aggregated Ni on the surface of the catalyst0The crystal phase is dispersed, and the catalytic performance of the catalyst is further improved. Finally, the existence of the water vapor can effectively reduce the temperature rise of the catalyst bed layer, slow down the reduction of the dispersion degree of the active components of nickel and copper, and simultaneously avoid the sintering of nickel and copper particles in a high-temperature environment. Meanwhile, in the presence of water vapor, due to the strong polarity of water, when competing with oxygen for adsorption, the water is preferentially adsorbed on the active sites of the catalyst, so that the contact probability of oxygen and carbon is reduced, the number of molecules of oxygen carbon burning reaction on the surface of the catalyst is reduced, the carbon burning reaction rate is slowed down, and the phenomenon of 'temperature runaway' can be inhibited.
(3) Finally, reduction treatment is carried out in a hydrogen atmosphere, and inactive copper nitride (Cu)3N) species to active copper species are dispersed on the catalyst surface. Meanwhile, the active component nickel can be further dispersed, so that the activity of the deactivated amination catalyst is completely recovered.
(4) The amination catalyst regenerated by the method can be used in amination reaction for preparing polyether amine by hydrogenating and aminating polyether polyol, and the catalytic performance of the regenerated catalyst reaches or is even better than that of a fresh catalyst.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the examples listed, and it should also include equivalent modifications and variations to the technical solutions defined in the claims appended to the present application.
Gas chromatograph: shimadzu GC-2014(FID) detector, SE-30 capillary column (phi 0.30mm x 30m), injection port 270 deg.C, detector 270 deg.C; temperature rising procedure: the temperature is kept constant at 70 ℃ for 1min, and then the temperature is increased to 240 ℃ at the speed of 40 ℃/min and kept for 5 min.
Hydroxyl value determination method: see GB/T12008.3-2009.
Method for determining total amine value: titrating the product by adopting 0.5mol/L hydrochloric acid solution, and calculating the total amine value of the product according to the mass of the consumed hydrochloric acid.
Conversion rate of raw material: the total amine value of the product/the total hydroxyl value of the raw material is multiplied by 100 percent.
The product yield is as follows: the mass of the polyetheramine product/the mass of the raw material polyether polyol is multiplied by 100%.
The reductive amination reactor in the examples is a fixed bed reactor.
Polyether polyol (PPG-230, D400, D-2000, D-5000, T-403): vanhua chemical group, Inc.
After 2000 hours of continuous operation the deactivated amination Catalyst, which was prepared according to the method described in CN106669731 (example 1), and which was numbered F-Catalyst, having the composition 16.5 wt% Ni, 5 wt% Cu, 1 wt% Pd, 2.5 wt% Cr, and the remainder alumina, was regenerated using the method described in the present invention to obtain the regenerated Catalyst Re-Catalyst.
The regenerated catalyst was evaluated by the evaluation method described in CN 106669731.
Example 1
(1) A washing step: according to the solid-liquid volume ratio of 1: 1 adding the deactivated catalyst into an acetic acid solution with the concentration of 5 wt%, heating and refluxing for 8 hours, filtering, washing to be neutral, and drying.
(2) And (3) roasting: placing an amination catalyst obtained by washing and drying treatment in a fixed bed reactor at normal pressure, heating to 400 ℃, wherein the heating rate is 3 ℃/min, and the solid-liquid volume ratio is 1: and (20) introducing a hydrogen peroxide solution with the concentration of 16wt% for charcoal burning regeneration, wherein the roasting time is 5h until no CO2 is detected to be generated in tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 200 ℃, the heating rate is 0.5 ℃/min, and the volume ratio is 1: and (3) fully reducing the mixed gas of hydrogen and nitrogen of 40 for 5 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-1.
Amination of polyether polyol PPG-230 (difunctional, molecular weight 230)
Filling 30ml of strip regenerated Catalyst Re-Catalyst-1 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 230 ℃, raising the system pressure to 25MPa and starting feeding, wherein the space velocity of PPG-230 is 2h-1, the molar ratio of liquid ammonia/PPG-230 is 40:1, and the molar ratio of hydrogen/PPG-230 is 0.3: 1, the reactant is distilled to remove excessive ammonia and water, and gas chromatography analysis is used for detecting that the content of the diamino product is 98.5 percent, the content of the mono-amino product is 0.5 percent, PPG-230 is not detected, and the content of other products is 1.0 percent. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 98.5 percent.
Example 2
(1) A washing step: according to the solid-liquid volume ratio of 1: 5 adding the deactivated catalyst into 30wt% acetic acid solution, heating and refluxing for 10h, filtering, washing to neutrality, and drying.
(2) And (3) roasting: placing an amination catalyst obtained by washing and drying treatment in a fixed bed reactor at normal pressure, heating to 300 ℃, wherein the heating rate is 1 ℃/min, and the solid-liquid volume ratio is 1: and (3) introducing 20wt% hydrogen peroxide solution into the tail gas, carrying out charcoal burning regeneration for 10h until no CO2 is detected to be generated in the tail gas, and cooling to obtain the calcined and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 100 ℃, the heating rate is 0.8 ℃/min, and the volume ratio is 1: and (3) fully reducing the 10 hydrogen/nitrogen mixed gas for 15 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-2.
Amination of polyether polyol D-2000 (difunctional, molecular weight 2000)
Filling 30ml of strip-shaped regenerated Catalyst Re-Catalyst-2 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 300 ℃, raising the system pressure to 30MPa and starting feeding, wherein the space velocity of D-2000 is 3h < -1 >, the molar ratio of liquid ammonia to D-2000 is 20:1, and the molar ratio of hydrogen to D-2000 is 0.01: 1, the reactant is distilled to remove excessive ammonia and water, and the gas chromatography analysis is used for detecting that the content of the diamino product is 94.5 percent, the content of the mono-amino product is 5 percent, the D-2000 is not detected, and the content of other products is 0.5 percent. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 94.5 percent.
Example 3
(1) A washing step: according to the solid-liquid volume ratio of 1: 8, adding the deactivated catalyst into an acetic acid solution with the concentration of 20wt%, heating and refluxing for 5 hours, filtering, washing to be neutral, and drying.
(2) And (3) roasting: placing an amination catalyst obtained by washing and drying treatment in a fixed bed reactor at normal pressure, heating to 450 ℃, wherein the heating rate is 5 ℃/min, and the solid-liquid volume ratio is 1: 30 introducing 15 wt% hydrogen peroxide solution for charcoal burning regeneration, wherein the roasting time is 8h until no CO2 is detected in tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 250 ℃, the heating rate is 1 ℃/min, and the volume ratio is 1: and (3) fully reducing the hydrogen/nitrogen mixed gas of 20 for 8 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-3.
Amination of polyether polyol T-403 (trifunctional, molecular weight 440)
Filling 30ml of strip-shaped regenerated Catalyst Re-Catalyst-3 with the diameter of 3mm in a fixed bed reactor, raising the reaction temperature to 220 ℃, raising the system pressure to 18MPa and starting feeding, wherein the space velocity of T-403 is 1.5h < -1 >, the molar ratio of liquid ammonia to T-403 is 8:1, and the molar ratio of hydrogen to T-403 is 0.02: 1, the reactant is distilled to remove excessive ammonia and water, and the content of the triamino product is 97.5 percent, the content of the diamino product is 2 percent, the monoamino product and T-403 are not detected, and the content of other products is 0.5 percent by using gas chromatography analysis. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 97.5 percent.
Example 4
(1) A washing step: according to the solid-liquid volume ratio of 1: 10 adding the deactivated catalyst into an acetic acid solution with the concentration of 15 wt%, heating and refluxing for 3h, filtering, washing to be neutral, and drying.
(2) And (3) roasting: placing an amination catalyst obtained by washing and drying treatment in a fixed bed reactor at normal pressure, heating to 600 ℃, wherein the heating rate is 4 ℃/min, and the solid-liquid volume ratio is 1: 35 introducing a hydrogen peroxide solution with the concentration of 12 wt% for charcoal burning regeneration, wherein the roasting time is 1h until no CO2 is detected to be generated in the tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 300 ℃, the heating rate is 2 ℃/min, and the volume ratio is 1: and (3) fully reducing the mixed gas of 50 hydrogen and nitrogen for 1 hour, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-4.
Amination of polyether polyol D-5000 (difunctional, molecular weight 5000)
Filling 30ml of spherical regenerated Catalyst Re-Catalyst-4 with the diameter of 3mm in a fixed bed reactor, raising the reaction temperature to 250 ℃, raising the system pressure to 20MPa and starting feeding, wherein the space velocity of D-5000 is 2.5h < -1 >, the molar ratio of liquid ammonia to D-5000 is 3:1, and the molar ratio of hydrogen to T-403 is 0.01: 1, the reactant is distilled to remove excessive ammonia and water, and the content of a diamino product is 99.5 percent, the content of a mono-amino product and D-5000 are not detected and the content of other products is 0.5 percent by using gas chromatography analysis. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 99.5 percent.
Example 5
(1) A washing step: according to the solid-liquid volume ratio of 1: 20 adding the deactivated catalyst into 10 wt% acetic acid solution, heating and refluxing for 1h, filtering, washing to neutrality, and drying.
(2) And (3) roasting: placing an amination catalyst obtained by washing and drying treatment in a fixed bed reactor at normal pressure, heating to 200 ℃, wherein the heating rate is 10 ℃/min, and the solid-liquid volume ratio is 1: and 10, introducing a hydrogen peroxide solution with the concentration of 10 wt% for charcoal burning regeneration, wherein the roasting time is 15 hours until no CO2 is detected to be generated in tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 400 ℃, the heating rate is 0.1 ℃/min, and the volume ratio is 1: and (3) fully reducing the mixed gas of 50 hydrogen and nitrogen for 1 hour, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-5.
Amination of polyether polyol D-400 (difunctional, molecular weight 430)
Filling 30ml of strip regenerated Catalyst Re-Catalyst-5 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 210 ℃, raising the system pressure to 20MPa and starting feeding, wherein the space velocity of D-400 is 1.5h-1The molar ratio of liquid ammonia to D-400 is 30:1, and the molar ratio of hydrogen to D-400 is 0.2: 1, excessive ammonia and water are removed from the reactants by distillation, and the content of a diamino product is 97.6 percent, the content of a mono-amino product is 1.4 percent, D-400 is not detected and the content of other products is 1.0 percent by gas chromatography analysis. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 97.6 percent.
Comparative example 1
This example differs from example 1 in that the regeneration of the deactivated catalyst is carried out only by washing regeneration.
(1) A washing step: according to the solid-liquid volume ratio of 1: 1 adding the deactivated catalyst into an acetic acid solution with the concentration of 5 wt%, heating and refluxing for 8 hours, filtering, washing to be neutral, and drying.
(2) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 200 ℃, the heating rate is 0.5 ℃/min, and the volume ratio is 1: and (3) fully reducing the mixed gas of hydrogen and nitrogen of 40 for 5 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-6.
Amination of polyether polyol PPG-230 (difunctional, molecular weight 230)
Filling 30ml of strip regenerated Catalyst Re-Catalyst-6 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 230 ℃, raising the system pressure to 25MPa and starting feeding, wherein the space velocity of PPG-230 is 2h-1The molar ratio of liquid ammonia to PPG-230 is 40:1, and the molar ratio of hydrogen to PPG-230 is 0.3: 1, distilling the reaction product to remove excessive ammonia and water, and analyzing by gas chromatography to obtain the content of the diamino product70.5 percent, the content of the mono-amination product is 20.5 percent, PPG-230 is not detected, and the content of other products is 9.0 percent. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 70.5 percent.
Comparative example 2
This example differs from example 2 in that the regeneration of the deactivated catalyst is carried out only by calcination.
(1) And (3) roasting: under normal pressure, putting the deactivated catalyst in a fixed bed reactor, heating to 450 ℃, wherein the heating rate is 5 ℃/min, and the solid-liquid volume ratio is 1: 30 introducing 15 wt% hydrogen peroxide solution for charcoal burning regeneration, wherein the roasting time is 8h until no CO2 is detected in tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(2) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 250 ℃, the heating rate is 1 ℃/min, and the volume ratio is 1: and (3) fully reducing the hydrogen/nitrogen mixed gas of 20 for 8 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-7.
Amination of polyether polyol D-2000 (difunctional, molecular weight 2000)
Filling 30ml of strip-shaped regenerated Catalyst Re-Catalyst-7 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 300 ℃, raising the system pressure to 30MPa and starting feeding, wherein the space velocity of D-2000 is 3h-1The molar ratio of liquid ammonia to D-2000 is 20:1, the molar ratio of hydrogen to D-2000 is 0.01: 1, the reactant is distilled to remove excessive ammonia and water, and the gas chromatography analysis shows that the content of the diamino product is 85.5 percent, the content of the mono-amino product is 10.5 percent, the D-2000 is not detected, and the content of other products is 4.0 percent. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 85.5 percent.
Comparative example 3
This example differs from example 1 in that no hydrogen peroxide solution is used in the deactivated catalyst calcination step.
(1) A washing step: according to the solid-liquid volume ratio of 1: 1 adding the deactivated catalyst into an acetic acid solution with the concentration of 5 wt%, heating and refluxing for 8 hours, filtering, washing to be neutral, and drying.
(2) And (3) roasting: and (3) placing the deactivated catalyst in a fixed bed reactor under normal pressure, heating to 450 ℃, heating at a rate of 5 ℃/min, and roasting for 8h until no CO2 is detected in tail gas, and cooling to obtain the roasted and regenerated amination catalyst.
(3) A reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 200 ℃, the heating rate is 0.5 ℃/min, and the volume ratio is 1: and (3) fully reducing the mixed gas of hydrogen and nitrogen of 40 for 5 hours, and cooling to obtain the reductive and regenerated amination Catalyst Re-Catalyst-8.
Amination of polyether polyol PPG-230 (difunctional, molecular weight 230)
Filling 30ml of strip regenerated Catalyst Re-Catalyst-8 with the diameter of 2mm in a fixed bed reactor, raising the reaction temperature to 230 ℃, raising the system pressure to 25MPa and starting feeding, wherein the space velocity of PPG-230 is 2h-1The molar ratio of liquid ammonia to PPG-230 is 40:1, and the molar ratio of hydrogen to PPG-230 is 0.3: 1, excessive ammonia and water are removed from the reactants by distillation, and the content of a diamino product is 72.2 percent, the content of a mono-amino product is 19.6 percent, PPG-230 is not detected and the content of other products is 8.2 percent by using gas chromatography analysis. After 300h, sampling and analyzing, the result is unchanged, the conversion rate of the raw material is 100 percent, and the yield of the aminated product is 72.2 percent.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes or modifications of the technical solution of the present invention are within the spirit of the present invention.

Claims (14)

1. A process for regenerating an amination catalyst used in the hydroamination of polyether polyols to produce polyether amines, which process comprises:
(A) adding the inactivated amination catalyst into an organic acid solution, heating and refluxing, filtering, washing to be neutral, and drying;
(B) carrying out charcoal burning regeneration on the amination catalyst obtained by washing and drying treatment in the presence of hydrogen peroxide to obtain a roasted and regenerated amination catalyst;
(C) reducing the roasted and regenerated amination catalyst by using hydrogen to obtain a reduced and regenerated amination catalyst;
the amination catalyst takes alumina as a carrier, more than two metals selected from Ni, Co, Cu and Pd as active components, and more than one metal selected from Zr, Cr, Mo, Fe, Zn, Sn, Ce, Mg, Mn, La, Hf, Sr, V, W, Pb, Pt, Ag, Rh, Ru, Bi, Nd, Sb and Be or oxides thereof as an auxiliary agent.
2. The regeneration method according to claim 1, wherein the concentration of the organic acid solution is 5 to 30wt%, and the organic acid solution is one or more selected from a formic acid solution, an acetic acid solution, a tartaric acid solution, and an oxalic acid solution.
3. The regeneration method according to claim 1 or 2, wherein the organic acid solution is an acetic acid solution having a concentration of 10 to 20 wt%.
4. Regeneration process according to claim 1 or 2, wherein the volume ratio of deactivated amination catalyst to organic acid solution is 1: 1-20.
5. Regeneration process according to claim 1 or 2, wherein the volume ratio of deactivated amination catalyst to organic acid solution is 1: 5-10.
6. Regeneration process according to claim 1 or 2, wherein the heating reflux time is 1-10 h.
7. Regeneration process according to claim 1 or 2, wherein the heating reflux time is 3-8 h.
8. The regeneration method according to claim 1 or 2, wherein in the step (B), the amination catalyst obtained by washing and drying treatment is subjected to a solid-liquid volume ratio of 1: introducing hydrogen peroxide solution with the concentration of 3-30wt% into the reactor 10-50 to carry out charcoal burning regeneration, wherein the burning time is 1-15 h.
9. The regeneration process according to claim 8, wherein the calcination time is 5-10 h.
10. The regeneration method according to claim 1 or 2, wherein, in the step (C), the regeneration is carried out at 100 ℃ and 400 ℃ in a volume ratio of 1: reducing the mixed gas of hydrogen and nitrogen of 1-100 parts for 1-20 hours, and cooling to ambient temperature.
11. A process for regenerating an amination catalyst used in the hydroamination of polyether polyols to produce polyether amines, which process comprises:
a washing step: according to the solid-liquid volume ratio of 1: 1-20, adding the inactivated amination catalyst into an organic acid solution with the concentration of 5-30wt%, heating and refluxing for 1-10h, filtering, washing to be neutral, and drying;
and (3) roasting: at normal pressure, placing the amination catalyst obtained by washing and drying treatment in a fixed bed reactor, heating to 200-600 ℃, wherein the heating rate is 1-10 ℃/min, and the solid-liquid volume ratio is 1: introducing 3-30wt% hydrogen peroxide solution 10-50 for charcoal-burning regeneration for 1-15 hr until no CO is detected in tail gas2Generating and cooling to obtain an amination catalyst after roasting and regeneration;
a reduction step: under normal pressure, the temperature of the fixed bed reactor is raised to 100-400 ℃, the heating rate is 0.1-2 ℃/min, and the volume ratio is 1: 1-100 of hydrogen/nitrogen mixed gas is fully reduced for 1-20 hours, and the temperature is reduced, thus obtaining the amination catalyst after reduction and regeneration;
the amination catalyst takes alumina as a carrier, more than two metals selected from Ni, Co, Cu and Pd as active components, and more than one metal selected from Zr, Cr, Mo, Fe, Zn, Sn, Ce, Mg, Mn, La, Hf, Sr, V, W, Pb, Pt, Ag, Rh, Ru, Bi, Nd, Sb and Be or oxides thereof as an auxiliary agent.
12. The regeneration method according to claim 11, wherein, in the calcination step, the concentration of the hydrogen peroxide solution is 10 to 20 wt%; solid-liquid volume ratio 1: 20-35; and/or the roasting temperature is 300-450 ℃, the heating rate is 3-5 ℃/min, and the roasting time is 5-10 h.
13. The regeneration method as claimed in claim 12, wherein the concentration of the hydrogen peroxide solution in the calcination step is 12 to 16 wt%.
14. The regeneration method as claimed in any one of claims 11 to 13, wherein the reduction temperature is 200-: 10-80.
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