CN108395528B - polyether polyols and preparation method thereof, polyether amines and prepared polyether amines - Google Patents

polyether polyols and preparation method thereof, polyether amines and prepared polyether amines Download PDF

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CN108395528B
CN108395528B CN201810057193.2A CN201810057193A CN108395528B CN 108395528 B CN108395528 B CN 108395528B CN 201810057193 A CN201810057193 A CN 201810057193A CN 108395528 B CN108395528 B CN 108395528B
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catalyst
polyether
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polyether polyol
polypropylene glycol
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CN108395528A (en
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任树杰
张聪颖
刘振国
李鑫
李文滨
曹善健
尚永华
黎源
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Wanhua Chemical Group Co Ltd
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    • 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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    • B01J27/0573—Selenium; Compounds thereof
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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with 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
    • C08G65/26—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 from cyclic ethers and other compounds
    • C08G65/2642—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 from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2648—Alkali metals or compounds thereof
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    • 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
    • C08G65/322—Polymers modified by chemical after-treatment with inorganic compounds containing hydrogen
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C08G65/3255—Ammonia
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping

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  • Polyethers (AREA)

Abstract

The invention discloses polyether polyols and a preparation method thereof, polyether amines and a preparation method thereof, wherein polypropylene glycol rectification byproducts (including propylene glycol, dipropylene glycol and dipropylene glycol) are used as raw materials to prepare anti-yellowing polyether polyols, the preparation process is carried out in the presence of N, N-dialkyl hydroxylamine, the anti-yellowing polyether polyols are reacted under the action of a reductive amination catalyst to prepare the polyether amines, and the reductive amination catalyst comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2An active component. The invention changes waste into valuable, solves the problem that polyether polyol synthesized by recycled polypropylene glycol rectification byproducts is easy to yellow, and finally prepares a polyether amine product with the Pt-Co color number below 10.

Description

polyether polyols and preparation method thereof, polyether amines and prepared polyether amines
Technical Field
The invention relates to polyether polyols, a preparation method thereof, a method for preparing polyether amine by using the polyether polyols and the prepared polyether amine, in particular to methods for preparing anti-yellowing polyether polyols by using byproducts and a method for preparing polyether amine by using the polyether polyols.
Background
Polyether polyols of different functionality can be prepared by reacting hydroxyl-containing initiators with alkylene oxides, such as ethylene oxide and propylene oxide, in the presence of alkali metal hydroxide catalysts, the most common polyether polyols being polyoxypropylene glycols and polyoxypropylene triols, polyether polyols are important high molecular weight materials, and since the 20 th 60 s polyurethane articles produced therefrom have been used in a wide range of furniture, insulation, refrigerators and other areas.
US4751331 discloses methods for decolorizing polyether polyols having a yellow color comprising heating polyether polyols in the presence of water and air to a temperature of from about 95 ℃ to the decomposition temperature of the polyether polyol sufficient to measurably reduce the color of the polyether polyol preferred initiators in the patent include alkylene glycols such as ethylene glycol, propylene glycol and 1, 4-butanediol, glycerol, trimethylolpropane, low molecular weight polyfunctional polyethers, alkylene diamines, sugars such as sucrose and sorbitol, bisphenols, alkanolamines, and the like.
CN107400229 discloses anti-yellowing polyether polyols and a preparation method thereof, wherein aliphatic polyols are used as main bodies, and are compounded with hydrogen-containing triazine compounds and hydroxyl-containing phosphite compounds to form a composite initiator, and the composite initiator is prepared by ring-opening polymerization with propylene oxide and/or ethylene oxide under the action of a catalyst, and the durability of anti-yellowing is enhanced by introducing reactive antioxidant and anti-ultraviolet polyether polyols.
In the prior art for preparing the anti-yellowing polyether polyol, no patent report is found for preparing the anti-yellowing polyether polyol by ring-opening polymerization of a polypropylene glycol rectification byproduct serving as an initiator and propylene oxide under the action of an alkaline catalyst and an antioxidant N, N-dialkyl hydroxylamine.
The polyether amine (PEA) is a polymer with -class main chain as a polyether structure and active functional groups at the tail end as amino groups, can be widely applied to the fields of epoxy resin curing agents, wind energy blade curing agents, polyurethane polyurea elastomers, gasoline cleaning agents, water-based coatings, textile finishing agents, epoxy toughening and the like.
Under the same reductive amination conditions, as polyether part with lower activity undergoes reductive amination reaction, polyether part with higher activity is easy to undergo chain breakage, thereby reducing the product yield.
US4014933 discloses alumina or silica supported Co-Ni-Cu catalysts comprising 10% Co, 10% Ni, 4% Cu and 0.4% phosphoric acid, the balance being Al and a process for the amination of polypropylene glycols2O3. The catalyst is suitable for amination reaction of polyether polyol with molecular weight greater than 1400.
US4152353 and US4153581 disclose alumina supported Ni, Cu and 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. The catalyst has the problems of low activity and poor selectivity.
US4209424 discloses alumina supported transition metal amination catalysts comprising or two of Ni, Co and Cu, wherein the metal content is 30-70%, the remainder being Al, and their use for the amination of polyether polyols2O3。
US4973761 discloses alumina supported Ni, Co and Cu amination catalysts and their use in the amination of polytetrahydrofuran ether glycol, the catalysts are suitable for the amination of polyether polyols with molecular weight between 640-4000, and have the problems of low catalyst activity and poor product selectivity.
US5003107 discloses alumina supported Ni, Cu, Cr, Mo amination catalysts and their use in the amination of polyoxytetramethylene glycol comprising 70-75% Ni, 20-25% Cu, 0.5-5% Cr and 1-5% Mo, the remainder being 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 the amination of polyether polyols having a molecular weight of less than 500.
CN102780571 discloses 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。
CN106669731 discloses Al2O3A preparation method of a supported catalyst. Based on the total amount of the catalyst, the active component Ni content is 5-30 wt%, 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 supported 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 raw material impurities, 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, carbon deposition, blockage, sintering, heat deactivation and the like.
US5352835 discloses a process for preparing mechanically stable phase alumina supported catalysts comprising, based on the total catalyst, Ni 15-30%, Cu 3-20%, Mo 0.5-1%, and theta-Al as the carrier2O3. The carrier is composed of gamma-Al2O3Is obtained by high-temperature roasting, and has better stability. However, the catalyst preparation process has the following problems: (1) the pore size distribution of the carrier is strict, and the difficulty in preparing the carrier meeting the requirements is high. (2) The preparation is carried out by a molten salt method, and the problem of carrier pore channel blockage caused by salting out exists in the dipping process. (3) The metal loading is high, the metal is dispersed unevenly, and the problems of difficult preparation and metal loss exist.
US20140179952 discloses CoO-Y species2O3The catalyst has CoO content of 57-90 wt% and Y content2O3The content of (A) is 9-17%, and the content of PdO is 0.9-25.7%. The patent states that cobalt and yttrium in the catalyst have a higher affinity for amine compounds and hydrogen than for water, and therefore the catalyst has better stability. However, the catalyst has the following problems: (1) the coprecipitation method is adopted for preparing the material, so that the problems of complex process and poor reproducibility exist. (2) The catalyst contains high content of cobalt, rare metal yttrium and noble metal palladium, and the content of active components in the supported catalyst is up to 50 percent (by weight), so the problem of high catalyst cost exists. (3) The catalyst is only used in batch process, and does not relate to application examples of continuous process.
In the epoxy application field, the polyetheramine can be applied to epoxy terraces, ornament adhesives, wind power, coatings, potting materials, composite materials, adhesives and the like, colorless and transparent high-gloss materials cannot be obtained from epoxy resin solidified by the polyetheramine with high color number, and the application of the polyetheramine in the casting and potting fields is limited, meanwhile, the polyetheramine with high color number is also limited by in the epoxy terraces, ornament adhesives and wind power fields.
Disclosure of Invention
In order to solve the problems, aims to provide anti-yellowing polyether polyols and a preparation method thereof, in the method, polypropylene glycol rectification byproducts are used as raw materials, so that the utilization rate of the raw materials is improved, the production cost is reduced, the environmental pollution is reduced, and the problem that polyether polyols synthesized by recycled polypropylene glycol rectification byproducts are easy to yellow is solved.
Another purposes of the invention are to provide polyether amines and a preparation method thereof, wherein the anti-yellowing polyether polyol is used as a raw material and is subjected to reductive amination under the action of an improved catalyst, and the prepared polyether amine has the advantages of low color number and good selectivity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of anti-yellowing polyether polyols comprises the following steps:
(1) putting the polypropylene glycol rectification by-product, the alkaline catalyst and the N, N-dialkyl hydroxylamine into a reaction kettle, dehydrating, continuously adding propylene oxide, carrying out polymerization reaction at the reaction temperature of 100-150 ℃ and the relative pressure of less than or equal to 0.3MPa, and aging for 1-5 hours after the propylene oxide is added;
(2) and (2) reducing the temperature of the product obtained in the step (1) to 50-80 ℃, adding quantitative water, inorganic acid and adsorbent into the system, stirring for 20-60 min, dehydrating, and filtering to obtain the polyether polyol.
In the step (1), the polypropylene glycol initiator is propylene glycol, and the polymerization unit is propylene oxide.
Preferably, the dehydration condition in the step (1) of the invention is dehydration for 30-70 min at 80-120 ℃ and relative pressure of-0.08-0.1 MPa.
The number average molecular weight of the polypropylene glycol in the step (1) is 100 to 1000, preferably 150 to 500, and more preferably 200 to 300.
In the step (1), the polypropylene glycol rectification by-product is extracted from the top of the polypropylene glycol rectification tower, and the by-product comprises the following components: based on the weight of the by-product,
0.5-5% of propylene glycol, preferably 1-3%;
dipropylene glycol 80-95%, preferably 85-91%;
4-15% of tripropylene glycol, preferably 6-12%.
The alkaline catalyst in step (1) of the present invention is selected from sodium hydroxide and/or potassium hydroxide, preferably potassium hydroxide.
The amount of the basic catalyst used in step (1) of the present invention is 0.1 to 1 wt%, preferably 0.4 to 0.8 wt%, based on the weight of the by-product of polypropylene glycol rectification.
The N, N-dihydrocarbylhydroxylamine in step (1) of the present invention is selected from N, N-diethylhydroxylamine and/or N, N-dibenzylhydroxylamine, preferably N, N-diethylhydroxylamine.
In the step (1), the amount of the N, N-dihydrocarbylhydroxylamine is 5 to 500ppm, preferably 20 to 300ppm, and more preferably 50 to 100ppm, based on the weight of the by-product of the polypropylene glycol rectification.
The adding amount of the water in the step (2) is 0.5-5 wt%, preferably 2-4 wt%, calculated by taking the weight of the polypropylene glycol rectification by-product as a reference.
In the step (2) of the present invention, the inorganic acid is selected from hydrochloric acid, phosphoric acid and sulfuric acid, preferably 85 wt% phosphoric acid.
In the step (2), the molar ratio of the inorganic acid to the basic catalyst is 0.1-2, preferably 0.5-1.5, and more preferably 0.8-1.2.
The adsorbent in step (2) of the present invention is selected from bentonite, montmorillonite and magnesium silicate, preferably magnesium silicate.
The adding amount of the adsorbent in the step (2) is 0.01-1 wt%, preferably 0.2-0.6 wt%, calculated by taking the weight of the polypropylene glycol rectification by-product as a reference.
Preferably, the dehydration condition in the step (2) of the invention is that the temperature is 100-140 ℃, the relative pressure is-0.08-0.1 MPa, and the dehydration lasts for 0.5-2 h until the water content of the system is less than or equal to 0.05%.
The number average molecular weight of the polyether polyol prepared in the step (2) is 100-1000, preferably 150-500, and more preferably 200-300.
The color number of Pt-Co of the polyether polyol obtained in the step (2) is 1-10, and preferably 4-8.
method for preparing polyether amine, comprising the following steps of carrying out hydroamination reaction on the anti-yellowing polyether polyol under the action of a reductive amination catalyst to prepare polyether amine.
According to the method for preparing the polyether amine, a continuous fixed bed process is preferably adopted, ammonia with the molar weight 5-30 times that of the anti-yellowing polyether polyol is introduced, hydrogen with the molar weight 0.1-10 times that of the anti-yellowing polyether polyol is introduced, and the hydroamination reaction is carried out at the reaction temperature of 180-240 ℃ and the absolute reaction pressure of 10.0-18.0 MPa.
The reductive amination catalyst comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2An active component.
Wherein the content of NiO is 2-15 wt%, preferably 5-10 wt% based on the weight of the catalyst; au coating2O3The content of (B) is 0.1-2 wt%, preferably 0.5-1.5 wt%; SeO2The content of (A) is 0.05-1 wt%, preferably 0.1-0.5 wt%; NbAlO4The content is 84 to 95 wt%, preferably 89 to 93 wt%.
The preparation method of the reductive amination catalyst comprises the following steps: according to the proportion,
(a) preparation of NbAlO4Carrier: uniformly mixing a niobium-containing compound and alumina, drying, roasting, forming to obtain a carrier, optionally grinding and screening before drying;
(b) preparing a catalyst: soaking the carrier obtained in the step (a) in an aqueous solution containing soluble nickel salt, gold salt and selenium-containing compound, drying after adsorption balance, and roasting to obtain a catalyst; the impregnation step is preferably an equal volume impregnation.
The niobium-containing compound of the present invention is or more selected from niobium nitrate, niobium sulfate, niobium hydroxide, niobium oxalate and niobium carbonate, preferably niobium hydroxide and/or niobium oxalate.
The nickel salt of the invention is selected from or more of nickel sulfate, nickel nitrate and nickel acetate of nickel, and nickel nitrate is preferred.
The gold salt is selected from or more of gold nitrate, gold chloride and chloroauric acid, and is preferably gold nitrate.
The selenium-containing compound is or more selected from selenious acid, sodium selenite, potassium selenite and selenium oxychloride, preferably selenious acid.
In the step (a), the drying temperature is 100-200 ℃, preferably 120-150 ℃, and the drying time is 4-24 hours, preferably 8-16 hours.
In the step (a), the roasting temperature is 700-1500 ℃, and preferably 900-1100 ℃; the roasting time is 10-40 h, preferably 20-30 h.
In the screening process in the step (a), the mesh number of the solid powder is controlled within the range of 100-200 meshes.
In the step (b), the drying temperature is 70-150 ℃, preferably 90-130 ℃, and the drying time is 2-12 hours, preferably 4-8 hours.
In the step (b), the roasting temperature is 100-600 ℃, preferably 300-500 ℃, and the roasting time is 1-24 hours, preferably 8-16 hours.
Of course, those skilled in the art understand that before the catalytic synthesis of the polyether amine, the catalyst needs to be subjected to reduction activation treatment, for example, reduction activation is performed at about 220 ℃ under pure hydrogen-containing atmosphere, for example, reduction is performed for 2-24 h, preferably 8-16 h at 150-500 ℃, preferably 200-400 ℃ under hydrogen atmosphere.
In the present invention, "optionally" means performing or not performing the subsequent operation.
The invention has the beneficial effects that:
(1) the polypropylene glycol rectification by-product is recycled to synthesize the polyether polyol raw material, so that the raw material utilization rate is improved, the production cost is reduced, and the environmental pollution is reduced;
(2) the problem that polyether polyol synthesized by polypropylene glycol rectification byproducts recycled is easy to yellow is solved by introducing antioxidant N, N-dialkyl hydroxylamine in the preparation process of polyether polyol, so that the problem that the color number of polyether amine products obtained by steps of reductive amination of the polyether polyol is high is solved, and the Pt-Co color number of the obtained polyether amine products is less than 10;
(3) the polyether polyol synthesized by taking the propylene glycol as an initiator has wider molecular weight distribution, the polyether polyol raw material needs to be pre-rectified to remove light components and then is subjected to hydroamination to obtain a qualified polyether amine product, the polyether polyol synthesized by taking byproducts (comprising the propylene glycol, dipropylene glycol and tripropylene glycol) obtained by polypropylene glycol rectification as the initiator has the advantage of narrower molecular weight distribution, and the polyether polyol is directly subjected to hydroamination without pre-rectification to obtain the qualified polyether amine product, so that the process flow is simplified, and the energy consumption is reduced;
(4) in the reductive amination catalyst, NbAlO4The carrier has excellent hydration resistance; SeO2The introduction of the catalyst increases the dispersion degree, the active surface area and the anti-sintering performance of Ni and Au in the catalyst, thereby improving the activity and the selectivity of the catalyst; the introduction of Au is beneficial to hydrogen transfer, inhibits the oligomerization and polymerization of imine, and enhances the carbon deposition resistance of the catalyst. The catalyst has the advantages of low metal loading capacity, good hydration resistance, carbon deposition resistance and sintering resistance, and simple preparation process.
Detailed Description
The present invention will be further described in with reference to the following examples, but the present invention is not limited to the examples listed, and includes equivalent modifications and variations of the technical solutions defined in the claims attached to the present application.
The method for measuring the Pt-Co color number of the product comprises the following steps: see GBT 3143-82.
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.
Method for determining secondary/tertiary amine value: and mixing and stirring the product and salicylaldehyde with equal mass for 2 hours, titrating the product by adopting 0.5mol/L hydrochloric acid solution, and calculating the sum of secondary amine and tertiary amine values of the product according to the mass of consumed hydrochloric acid.
Primary amine selectivity ═ (total amine number-secondary/tertiary amine number)/total amine number × 100%.
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.
Pulse chemical adsorption method: mimmerriek (Shanghai) instruments Inc./Autochem II Chemisorption Analyzer.
X-ray diffraction analysis: shanghai Cibach instruments systems Limited/PANalytical X Pert3Powder。
The molecular weight distribution tester comprises Shimadzu 20AD- (CTO-20A) -RID10A, mobile phase THF, isocratic elution, quantitative method, area classification method, and PS correction curve relative correction.
The average molecular weight was represented by a polymer PDI of degrees, where smaller PDI values indicate narrower molecular weight distribution and larger PDI values indicate broader molecular weight distribution.
Example 1
(1)7wt％NiO-1wt％Au2O3-0.2wt％SeO2/NbAlO4Preparation of the catalyst
99.1g of Nb (OH)5And 28.5g of Al2O3Adding into mortar, mixing, grinding, sieving to obtain 100-200 mesh mixture, transferring into crucible, drying at 110 deg.C for 14 hr, and calcining at 1050 deg.C in air for 20 hr (heating)Rate: 3 ℃/min; the ramp rate refers to raising the temperature from room temperature to the final temperature at a defined rate per minute). Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 98%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
According to the content composition of the catalyst, the carrier is soaked in 29.7gNi (NO) by adopting an equal volume impregnation method3)3·6H2O、1.68gAu(NO3)3And 0.25gH2SeO3After adsorption equilibrium, drying at 110 ℃ for 6h, and then roasting at 450 ℃ in air for 11h to obtain the catalyst precursor of 7 wt% NiO-1 wt% Au2O3-0.2wt％SeO2/NbAlO4Wherein NbAlO4The content was 91.8 wt%.
(2) Preparation of polyether polyol PPG-230
Adding 500g of polypropylene glycol rectification by-products (wherein the content of propylene glycol is 0.5 wt%, the content of dipropylene glycol is 90 wt%, the content of tripropylene glycol is 9.5 wt%), 2.0g of KOH and 0.03g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 50min at 100 ℃ and the relative pressure of-0.09 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the reaction temperature of 110 ℃ and the relative pressure of less than or equal to 0.3MPa, aging for 3h after 336g of propylene oxide is added, reducing the reaction temperature of the system to 50 ℃, adding 12.5g of deionized water, 4.6g of 85 wt% of phosphoric acid and 2.5g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 100 ℃, the relative pressure of-0.1 MPa, dehydrating for 2h until the water content of the system is less than or equal to 0.05 wt%, and filtering to obtain the polyether polyol PPG-230 with the number average molecular weight, PDI being 1.02 and the color number-color number being 7.
(3) Preparation of polyetheramines
And (3) preparing polyether amine by hydroammoniating the polyether polyol PPG-230 in the step (2), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 10 hours at 280 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 210 ℃, increasing the pressure to 14.0MPa, stabilizing the system, and then adding NH with a molar ratio3Pumping the liquid flow of 15/PPG-230 into a reactor, and introducing hydrogen 5 times the molar weight of PPG-230After reaction periods, the catalyst is filtered, vacuum-pumped and distilled to obtain the polyetheramine product, and chemical analysis shows that the reaction conversion rate is 100.0 percent, the primary amine selectivity is 99.7 percent, the Pt-Co color number of the polyetheramine product is 6, and the catalyst is continuously operated for 1000 hours, sampled and analyzed, and the result is unchanged.
Comparative example 1
(1) Preparation of polyether polyol PPG-230
Adding 500g of polypropylene glycol rectification by-products (wherein the content of propylene glycol is 0.5 wt%, the content of dipropylene glycol is 90 wt%, and the content of tripropylene glycol is 9.5 wt%) and 2.0g of KOH into a 1L reaction kettle in sequence, dehydrating for 50min at 100 ℃ and under the relative pressure of-0.09 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the reaction temperature of 110 ℃ and under the relative pressure of less than or equal to 0.3MPa, aging for 3h, reducing the reaction temperature of the system to 50 ℃, adding 12.5g of deionized water, 4.6g of 85% phosphoric acid and 2.5g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 100 ℃, the relative pressure of-0.1 MPa, dehydrating for 2h until the water content of the system is less than or equal to 0.05 wt%, and filtering to obtain polyether polyol PPG-230 with the number-average molecular weight, wherein the PDI is 1.03, and the color number of the polyether polyol Pt-Co product is 300.
(2) Preparation of polyetheramines
And (2) preparing polyether amine by hydroammoniating the polyether polyol PPG-230 in the step (1), and evaluating by adopting a continuous method fixed bed process. The catalyst precursor obtained in step (1) of example 1 was reduced at 280 ℃ for 10 hours in a hydrogen gas stream (at atmospheric pressure). Naturally cooling the temperature in the reactor to 210 ℃, increasing the pressure to 14.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid flow of/PPG-230 is pumped into a reactor through a pump, hydrogen with 5 times of the molar weight of PPG-230 is pumped in, after reaction periods, the polyether amine product is obtained through filtration and vacuum distillation, chemical analysis shows that the reaction conversion rate is 100.0 percent, the selectivity of primary amine is 99.7 percent, the color number of the polyether amine product Pt-Co is 290, the catalyst is continuously operated for 1000 hours, and sampling analysis shows that the result is unchanged.
Comparative example 2
The PPG-230 of comparative example 1 according to the invention was treated using the method of example 1 of patent US 4751331.
200g of the PPG-230 of comparative example 1 and a small amount of deionized water were placed in a 500ml three-necked flask, and after heating to about 150 ℃ under normal pressure for 30min, the Pt-Co color number of the PPG-230 was determined to be 280, which was substantially unchanged.
Comparative example 3
The difference from example 1 is that the catalyst was prepared according to the method of preparation of the catalyst in example XIX of patent US5352835A, 19.9 wt% Ni-7.6 wt% Cu/Al2O3A catalyst. The polyether glycol PPG-230 prepared in the example 1 is used as a raw material to carry out hydroamination reaction, and after the catalyst is continuously operated for 200 hours, the activity is obviously reduced, the reaction conversion rate is 80%, and the primary amine selectivity is 96.0%. The extent of rehydration of the alumina component was estimated to be 35% by X-ray derivative spectroscopy using the integrated intensity of the boehmite peak to the theta alumina peak. The X-ray diffraction analysis of the catalyst after 1000h of continuous operation in example 1 shows that the catalyst support is still NbAlO with a purity of more than 98%4。
Therefore, the catalyst of the invention has excellent hydration resistance, and the stability of the catalyst of the invention is obviously superior to that of the prior art alumina supported catalyst.
Comparative example 4
7 wt% NiO-1 wt% Au was prepared according to the method of example 12O3-0.2wt％ZrO2/NbAlO4A catalyst.
According to the content composition of the catalyst, 100g of white powder in example 1 was tabletted and molded by an isovolumetric impregnation method to obtain 3 x 3mm of NbAlO4Impregnation of the columnar support with 29.7gNi (NO)3)3·6H2O、1.68gAu(NO3)3And 0.6gZr (NO)3)4·5H2Drying the O in an aqueous solution of O at 110 ℃ for 6h after adsorption equilibrium, and then roasting the O in air at 450 ℃ for 11h to obtain a catalyst precursor of 7 wt% NiO-1 wt% Au2O3-0.2wt％ZrO2/NbAlO4Wherein NbAlO4The content was 91.8 wt%.
The same process conditions as in example 1 were used for 7 wt% NiO to 1 wt% Au2O3-0.2wt％ZrO2/NbAlO4The catalyst is evaluated, and the result shows that the activity of the catalyst is obviously reduced after the catalyst is continuously operated for 500 hours, the reaction conversion rate is 85 percent, and the selectivity of primary amine is 96.5 percent.
It can be seen that the catalyst SeO of the invention2The introduction of (2) and the combination of a specific carrier increase the dispersion degree, the active surface area and the anti-sintering performance of Ni and Au in the catalyst, thereby improving the activity and the selectivity of the catalyst.
Example 2
(1)10wt％NiO-0.7wt％Au2O3-0.3wt％SeO2/NbAlO4Preparation of the catalyst
136.0g of Nb2(CO3)5And 28.5g of Al2O3Adding into mortar, mixing, grinding, sieving to obtain a mixture of 100 meshes and 200 meshes, transferring the mixture into a crucible, drying at 150 deg.C for 8h, and calcining at 900 deg.C in air for 24h (heating rate: 5 deg.C/min. Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 98%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
According to the content composition of the catalyst, the carrier is immersed into the catalyst containing 43.7g of Ni (NO) by an equal volume immersion method3)3·6H2O、1.21g Au(NO3)3And 0.39g H2SeO3After adsorption equilibrium, drying at 130 ℃ for 4h, and then calcining in air at 300 ℃ for 14h to obtain the catalyst precursor of 10 wt% NiO-0.7 wt% Au2O3-0.3wt％SeO2/NbAlO4Wherein NbAlO4The content was 89 wt%.
(2) Preparation of polyether polyol PPG-400
Adding 500g of polypropylene glycol rectification by-products (wherein the content of propylene glycol is 1 wt%, the content of dipropylene glycol is 95 wt%, the content of tripropylene glycol is 4 wt%), 4.0g of KOH and 0.05g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 30min at the temperature of 120 ℃ and the relative pressure of-0.08 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the temperature of 120 ℃ and the relative pressure of less than or equal to 0.3MPa, aging for 2h after 984g of propylene oxide is added, reducing the reaction temperature of the system to 80 ℃, adding 20g of deionized water, 11.5g of 85% phosphoric acid and 2g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 140 ℃, the relative pressure of-0.08 MPa, dehydrating for 0.5h until the water content of the system is less than or equal to 0.05 wt%, and filtering to obtain polyether polyol PPG-400 with the number average molecular weight, wherein the PDI is 1.04, and the color number average molecular weight of the polyether polyol Pt-.
(3) Preparation of polyetheramines
And (3) preparing polyether amine by carrying out hydroamination on the polyether polyol PPG-400 in the step (2), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 15h at 200 ℃ in a hydrogen gas flow (under normal pressure). Naturally raising the temperature in the reactor to 220 ℃, raising the pressure to 17.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid flow of/PPG-400 is pumped into a reactor through a pump, hydrogen with the mole amount of 1 time of PPG-400 is pumped in, after reaction time, the polyether amine product is obtained through filtering, vacuum distillation, chemical analysis shows that the reaction conversion rate is 100.0%, the selectivity of primary amine is 99.0%, the color number of the polyether amine product Pt-Co is 6, and the catalyst is continuously operated for 800h, sampled and analyzed, and the result is unchanged.
Comparative example 5
(1) Polyether polyol PPG-400 synthesized by taking propylene glycol as initiator
Adding 500g of propylene glycol, 4.0g of KOH and 0.05g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 30min at the temperature of 120 ℃ and under the relative pressure of-0.08 MPa, continuously adding propylene oxide, carrying out polymerization reaction at the reaction temperature of 120 ℃ and under the relative pressure of less than or equal to 0.3MPa, and aging for 2h after 2128g of propylene oxide is added. Reducing the reaction temperature of the system to 80 ℃, adding 20g of deionized water, 11.5g of 85 percent phosphoric acid and 2g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 140 ℃, controlling the relative pressure to be-0.08 MPa, dehydrating for 0.5h until the water content of the system is less than or equal to 0.05 weight percent, and filtering to obtain polyether polyol PPG-400 with the number average molecular weight of 400, wherein the PDI is 1.10, and the color number of the polyether polyol product Pt-Co is 8.
(2) Preparation of polyetheramines
And (2) preparing polyether amine by hydroammoniating the polyether polyol PPG-400 in the step (1), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 15h at 200 ℃ in a hydrogen gas flow (under normal pressure). Naturally raising the temperature in the reactor to 220 ℃, raising the pressure to 17.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid flow of/PPG-400 is pumped into a reactor through a pump, hydrogen with the mole amount of 1 time of PPG-400 is pumped in, after reaction time, the polyether amine product is obtained through filtering, vacuum distillation, chemical analysis shows that the reaction conversion rate is 100.0%, the selectivity of primary amine is 85.0%, the color number of the polyether amine product Pt-Co is 7, and the catalyst is continuously operated for 800h, sampled and analyzed, and the result is unchanged.
Example 3
(1)5wt％NiO-0.8wt％Au2O3-0.5wt％SeO2/NbAlO4Preparation of the catalyst
226.5g of Nb (NO)3)5And 28.5g of Al2O3Adding into mortar, mixing, grinding, sieving to obtain a mixture of 100-200 meshes, transferring into crucible, drying at 130 deg.C for 10 hr, and calcining in air at 1100 deg.C for 22 hr (heating rate: 4 deg.C/min. heating rate refers to heating from room temperature to final temperature at a certain rate per minute): 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 97%4). And extruding to obtain 3X 3mm strip-shaped carriers.
According to the content composition of the catalyst, the carrier is immersed into the catalyst containing 20.8g of Ni (NO) by an equal volume immersion method3)3·6H2O、1.32g Au(NO3)3And 0.62g H2SeO3After adsorption equilibrium, the catalyst was dried at 100 ℃ for 8 hours and then calcined at 400 ℃ in air for 12 hours to obtain a catalyst precursor of 5 wt%NiO-0.8wt％Au2O3-0.5wt％SeO2/NbAlO4Wherein NbAlO4The content was 93.7 wt%.
(2) Preparation of polyether polyol PPG-430
Adding 500g of polypropylene glycol rectification by-products (wherein the content of propylene glycol is 2 wt%, the content of dipropylene glycol is 85 wt%, the content of tripropylene glycol is 13 wt%), 3.0g of KOH and 0.035g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 70min at 80 ℃ and the relative pressure of-0.1 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the reaction temperature of 140 ℃ and the relative pressure of less than or equal to 0.3MPa, aging for 5h after 1064g of propylene oxide is added, reducing the reaction temperature of the system to 60 ℃, adding 17.5g of deionized water, 4.3g of 85% phosphoric acid and 3g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 110 ℃, the relative pressure of-0.095 MPa, dehydrating for 1.5h until the water content of the system is less than or equal to 0.05 wt%, and filtering to obtain polyether polyol PPG-430, PDI (PDI) (1.03) with the number-average molecular weight being 430, and the color number average molecular weight of the polyether.
(3) Preparation of polyetheramines
And (3) preparing polyether amine by hydroammoniating the polyether polyol PPG-430 in the step (2), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 8 hours at 400 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 215 ℃, boosting the temperature to 14.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid flow of/PPG-430 is pumped into a reactor through a pump, hydrogen with the mole amount 2 times that of PPG-430 is introduced, after periods of reaction time, the polyether amine product is obtained through filtration, vacuum distillation, chemical analysis shows that the reaction conversion rate is 99.8 percent, the selectivity of primary amine is 98.5 percent, the color number of the polyether amine product Pt-Co is 7, and the catalyst is continuously operated for 900 hours for sampling analysis, so the result is unchanged.
Example 4
(1)6wt％NiO-1.4wt％Au2O3-0.4wt％SeO2/NbAlO4Preparation of the catalyst
Mixing 301.3gNb (C)2HO4)5And 28.5g of Al2O3Adding into mortar, mixing, grinding, and sieving100-. Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity of more than 99%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
According to the content composition of the catalyst, the carrier is immersed into a catalyst containing 25.3g of Ni (NO) by an equal volume immersion method3)3·6H2O、2.35g Au(NO3)3And 0.50g H2SeO3After adsorption equilibrium, drying at 120 ℃ for 5h, and then roasting at 500 ℃ in air for 9h to obtain the catalyst precursor of 6 wt% NiO-1.4 wt% Au2O3-0.4wt％SeO2/NbAlO4Wherein NbAlO4The content was 92.2 wt%.
(2) Preparation of polyether polyol PPG-600
Adding 500g of polypropylene glycol rectification by-products (wherein the content of propylene glycol is 1.5 wt%, the content of dipropylene glycol is 88 wt%, the content of tripropylene glycol is 10.5 wt%), 2.5g of KOH and 0.04g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 40min at the temperature of 110 ℃ and the relative pressure of-0.095 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the reaction temperature of 130 ℃ and the relative pressure of less than or equal to 0.3MPa, aging for 4h after 1691g of propylene oxide is added, reducing the reaction temperature of the system to 70 ℃, adding 15g of deionized water, 10.3g of 85% phosphoric acid and 1g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 120 ℃, the relative pressure of-0.09 MPa, dehydrating for 1h until the water content of the system is less than or equal to 0.05 wt%, and filtering to obtain polyether polyol PPG-600, PDI (PDI) 1.05) and the polyether polyol product with the color number average molecular weight of 9.
(3) Preparation of polyetheramines
And (3) preparing polyether amine by hydroammoniating the polyether polyol PPG-600 in the step (2), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 8 hours at 400 ℃ in a hydrogen gas flow (under normal pressure). Naturally cooling the temperature in the reactor to 240 ℃, and increasing the pressure to11.0MPa, after the system is stabilized, the molar ratio NH is adjusted3The liquid flow of the PPG-600 is pumped into a reactor through a pump, hydrogen with the mole amount of 3 times of that of the PPG-600 is pumped in, after reaction periods, the polyether amine product is obtained through filtration and vacuum distillation, chemical analysis shows that the reaction conversion rate is 100.0 percent, the selectivity of primary amine is 98.5 percent, the color number of the polyether amine product Pt-Co is 8, the catalyst continuously runs for 950 hours, and sampling analysis shows that the result is unchanged.
Example 5
(1)9wt％NiO-0.6wt％Au2O3-0.1wt％SeO2/NbAlO4Preparation of the catalyst
186.4g of Nb2(SO4)5And 28.5g of Al2O3Adding into mortar, mixing, grinding, sieving to obtain a mixture of 100 meshes and 200 meshes, transferring into a crucible, drying at 120 deg.C for 16h, and calcining in air at 950 deg.C for 30h (heating rate: 3 deg.C/min. heating rate refers to heating from room temperature to final temperature at a certain rate per minute). Yield: 100g of white powder (X-ray diffraction analysis shows NbAlO with a purity higher than 97%4). Tabletting and forming to obtain 3X 3mm columnar carrier.
According to the content composition of the catalyst, the carrier is immersed into the catalyst containing 38.8g of Ni (NO) by an equal volume immersion method3)3·6H2O、1.03g Au(NO3)3And 0.13g H2SeO3After adsorption equilibrium, drying at 90 ℃ for 10h, and then roasting at 550 ℃ in air for 8h to obtain the catalyst precursor of 9 wt% NiO-0.6 wt% Au2O3-0.1wt％SeO2/NbAlO4Wherein NbAlO4The content was 90.3 wt%.
(2) Preparation of polyether polyol PPG-1000
Adding 500g of polypropylene glycol rectification by-products (wherein the propylene glycol content is 2.5 wt%, the dipropylene glycol content is wt%, the tripropylene glycol content is 5.5 wt%), 3.5g of KOH and 0.05g of N, N-diethylhydroxylamine into a 1L reaction kettle in sequence, dehydrating for 60min at 90 ℃ and the relative pressure of-0.085 MPa, continuously adding propylene oxide, then carrying out polymerization reaction at the reaction temperature of 150 ℃ and the relative pressure of less than or equal to 0.3MPa, aging for 1h after 3238g of propylene oxide is added, reducing the reaction temperature of the system to 75 ℃, adding 10g of deionized water, 12.1g of 85% phosphoric acid and 1.5g of magnesium silicate into the system, stirring for 30min, controlling the temperature of the reaction kettle at 130 ℃, the relative pressure of-0.085 MPa, dehydrating for 0.8h until the water content of the system is less than or equal to 0.05%, and filtering to obtain the polyether polyol with the number average molecular weight of PPG of 1000, PDI of 1.01 and the polyether polyol product Pt-Co color number of 5.
(3) Preparation of polyetheramines
And (3) preparing polyether amine by hydroammoniating the polyether polyol PPG-1000 in the step (2), and evaluating by adopting a continuous method fixed bed process. Before the catalyst is used, the catalyst is reduced for 16h at 350 ℃ in a hydrogen stream (under normal pressure). Naturally cooling the temperature in the reactor to 180 ℃, increasing the pressure to 13.0MPa, stabilizing the system, and then adding NH with a molar ratio3The liquid flow of/PPG-1000 is pumped into a reactor through a pump, hydrogen with the mole amount of 6 times of that of PPG-1000 is pumped in, after reaction periods, the liquid is filtered and distilled in vacuum to obtain a polyetheramine product, after chemical analysis, the reaction conversion rate is 99.0 percent, the selectivity of primary amine is 98.5 percent, the color number of the polyetheramine product Pt-Co is 5, and the catalyst is continuously operated for 980 hours for sampling analysis, so that the result is unchanged.
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 (21)

  1. A process for preparing polyether polyols comprising the steps of:
    (1) putting the polypropylene glycol rectification by-product, an alkaline catalyst and N, N-dialkyl hydroxylamine into a reaction kettle, dehydrating, adding propylene oxide, carrying out polymerization reaction at 100-150 ℃ and under the condition that the relative pressure is less than or equal to 0.3MPa, and aging for 1-5 h;
    (2) and (2) reducing the temperature of the product obtained in the step (1) to 50-80 ℃, adding water, inorganic acid and an adsorbent into the product, stirring, dehydrating and filtering to obtain the polyether polyol.
  2. 2. The method of claim 1, wherein the polypropylene glycol initiator is propylene glycol and the polymerized units are propylene oxide; the number average molecular weight is 100 to 1000.
  3. 3. The method according to claim 2, wherein the polypropylene glycol has a number average molecular weight of 150 to 500.
  4. 4. The method according to claim 3, wherein the polypropylene glycol has a number average molecular weight of 200 to 300.
  5. 5. The method according to claim 1, wherein the polypropylene glycol rectification by-product in step (1) comprises the following composition: based on the weight of the by-product,
    0.5-5% of propylene glycol;
    dipropylene glycol 80-95%;
    4-15% of tripropylene glycol.
  6. 6. The method according to claim 5, wherein the polypropylene glycol rectification by-product in step (1) comprises the following composition: based on the weight of the by-product,
    1-3% of propylene glycol;
    dipropylene glycol 85-91%;
    6-12 parts of tripropylene glycol.
  7. 7. The process according to claim 1, wherein in step (1) the N, N-dihydrocarbylhydroxylamine is selected from N, N-diethylhydroxylamine and/or N, N-dibenzylhydroxylamine.
  8. 8. The method according to claim 1, wherein the amount of N, N-dihydrocarbylhydroxylamine used in step (1) is 5 to 500ppm based on the weight of the by-product of the polypropylene glycol rectification.
  9. 9. The method according to claim 8, wherein the amount of N, N-dihydrocarbylhydroxylamine used in step (1) is 20 to 300ppm based on the weight of the by-product of the polypropylene glycol rectification.
  10. 10. The method according to claim 9, wherein the amount of the N, N-dihydrocarbylhydroxylamine used in the step (1) is 50 to 100ppm based on the weight of the by-product of the polypropylene glycol rectification.
  11. 11, polyether polyol prepared by the method of claim 1, wherein the polyether polyol has a Pt-Co color number of 1-10 and a number average molecular weight of 100-1000.
  12. 12. The polyether polyol according to claim 11, wherein the polyether polyol has a Pt-Co color number of 4 to 8 and a number average molecular weight of 150 to 500.
  13. 13. The polyether polyol according to claim 11, wherein the polyether polyol has a number average molecular weight of 200 to 300.
  14. 14, method for preparing polyether amine, which comprises the steps of using polyether polyol prepared by the method of any one of claims 1-10- or polyether polyol of any one of claims 11-13- as raw material, and reacting in the presence of reductive amination catalyst, ammonia and hydrogen to prepare polyether amine.
  15. 15. The process of claim 14 wherein said reductive amination catalyst comprises NbAlO4Carrier and NiO and Au supported on the carrier2O3And SeO2An active component.
  16. 16. The method of claim 15, wherein the reductive amination catalyst comprises the following composition: based on the weight of the catalyst,
    Figure FDA0002232072610000031
  17. 17. the method of claim 16, wherein the reductive amination catalyst comprises the following composition: based on the weight of the catalyst,
  18. 18. the method of claim 15, wherein the method of preparing the reductive amination catalyst comprises the steps of: according to the proportion,
    (a) preparation of NbAlO4Carrier: uniformly mixing a niobium-containing compound and alumina, drying, roasting, forming to obtain a carrier, optionally grinding and screening before drying;
    (b) preparing a catalyst: soaking the carrier obtained in the step (a) in an aqueous solution containing soluble nickel salt, gold salt and selenium-containing compound, drying after adsorption equilibrium, and roasting to obtain the catalyst.
  19. 19. The method of claim 18 wherein said impregnating step is an equal volume impregnation.
  20. 20, polyetheramines prepared according to the method of any of claims 14-19 or , characterized in that the polyetheramine has a Pt-Co color number of 10 or less.
  21. 21. The polyetheramine of claim 20, wherein the polyetheramine has a Pt-Co color number of 8 or less.
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US4751331A (en) * 1987-05-01 1988-06-14 The Dow Chemical Company Control of yellow color in polyether polyols
CN105399940A (en) * 2015-11-10 2016-03-16 万华化学集团股份有限公司 Preparation method of polyether amine
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US4751331A (en) * 1987-05-01 1988-06-14 The Dow Chemical Company Control of yellow color in polyether polyols
CN105399940A (en) * 2015-11-10 2016-03-16 万华化学集团股份有限公司 Preparation method of polyether amine
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