CN113881032B - Supported metal cyanide complex catalyst and preparation method and application thereof - Google Patents
Supported metal cyanide complex catalyst and preparation method and application thereof Download PDFInfo
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- CN113881032B CN113881032B CN202010617709.1A CN202010617709A CN113881032B CN 113881032 B CN113881032 B CN 113881032B CN 202010617709 A CN202010617709 A CN 202010617709A CN 113881032 B CN113881032 B CN 113881032B
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- 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
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- 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
- C08G65/2603—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
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- 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
- C08G65/2693—Supported catalysts
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Abstract
The application discloses a supported metal cyanide complex catalyst and a preparation method and application thereof, wherein the catalyst comprises a carrier and a metal cyanide complex supported on the carrier, wherein the metal cyanide complex is selected from double metal cyanide complex and/or multiple metal cyanide complex, the carrier is selected from molecular sieve, and the weight ratio of the metal cyanide complex to the carrier is 1 (0.1-1000), preferably 1 (1-100). The preparation method comprises the following steps: and adding the carrier in the process of preparing the metal cyanide complex, and drying and forming to obtain the supported metal cyanide complex catalyst. The supported metal cyanide complex catalyst well solves the defects that the metal cyanide complex has higher cost, is not easy to remove and cannot be reused. And can solve the environmental problem of exceeding the standard of the transition metal content caused by the deposition of the metal cyanide complex catalyst in the polyether production device.
Description
Technical Field
The present application belongs to the field of metal catalysts, in particular to supported multimetal catalysts, and in particular to supported metal cyanide complex catalysts for the preparation of polyether polyols.
Background
Polyether polyol is a substance containing more than two hydroxyl groups (-OH) in the molecule and containing ether groups, can react with polyisocyanate to prepare polyurethane, and has wide application. Polyether polyols are generally prepared by ring-opening polymerization of epoxy monomers using basic metal hydroxides (e.g., KOH) as catalysts. However, KOH causes isomerization side reactions to occur in the epoxy compound, thereby increasing the content of the monol having double bonds rather than hydroxyl groups at the polyol terminals.
Since the last sixty U.S. universal tire rubber company used double metal cyanide complex catalysts (DMC) to prepare polyether polyols, double metal catalysts have been reported in a number of documents, such as documents US3427256, US3427334, US5158922, US5470813, US5482908, US5627120, EP6755716, CN1221561C, and the like.
The bimetallic catalyst is far more active than KOH and the resulting polyether polyol has very low unsaturation. However, there is a general induction period with a certain time, and there is a phenomenon that the temperature rises too fast in the reaction start stage. Patent CN101302286A has been filed before, and a multi-metal (MMC) catalyst is disclosed, which solves the problems of long induction period and difficult control of reaction temperature.
However, DMC is costly, difficult to remove, and not reusable, and on industrial polymerization vessels, transition metal overstock and other environmental problems can be caused by long term accumulation of DMC catalyst.
The application is based on an independently developed MMC catalyst, and the MMC catalyst is loaded on a molecular sieve to prepare the loaded MMC catalyst. The catalyst has high activity, can be reused, is convenient to remove, and solves the problems well.
Disclosure of Invention
In order to solve the problems of high MMC cost, difficult removal and incapability of being reused in the prior art, the application provides a supported multi-metal catalyst, and can solve the environmental problem of excessive transition metal content caused by MMC catalyst deposition in a polyether production device.
It is an object of the present application to provide a supported metal cyanide complex catalyst comprising a support and a metal cyanide complex supported on the support, wherein the metal cyanide complex is selected from the group consisting of double metal cyanide complexes (DMC) and/or multimetal cyanide complexes.
The double metal cyanide complex is not particularly limited, and may be selected from any double metal cyanide complex (DMC catalyst) disclosed in the prior art.
In a preferred embodiment, the multimetal cyanide complex has the general formula shown in formula (I):
M 1 a [M 2 d (CN) f ].M 1 b [M 3 e (CN) g ].M 1 c X h .Y i .Z j .kH 2 o is of formula (I);
wherein, in formula (I):
M 1 、M 3 independently selected from Zn, fe, ni, mn, co, sn, ph, mo, al, V, sr, W, cu or Cr, M 2 Selected from Fe, co, cr, mn, ir, ni, rh, ru or V, and M 1 、M 2 And M 3 Different from each other; and/or
X is selected from halogen element, CN - 、SCN - 、NO 3 - 、CO 3 2- 、SO 4 2- Or ClO 3 2- The method comprises the steps of carrying out a first treatment on the surface of the And/or
Y is selected from organic alcohols, preferably from C 4 ～C 10 An organic alcohol; and/or
Z is selected from aliphatic esters, aromatic monoesters or aromatic diesters; and/or
a. b, c, d, e, f, g, h, i, j, k are each independently selected from 0.1 to 20.
Wherein a, b, c represent M 1 D, e respectively represent M 2 、M 3 Wherein f and g represent the number of CN ions, H, i, j, k represents X, Y, Z and H, respectively 2 Number of O.
In a further preferred embodiment, in formula (I):
M 1 preferably Zn, ni or Co; and/or
M 3 Selected from Zn or Fe; and/or
M 2 Selected from Fe or Co; and/or
Y is preferably selected from tert-butanol or tert-amyl alcohol; and/or
Z is preferably selected from aromatic diesters, preferably phthalate esters and/or dibutyl phthalate esters; and/or
a. b, c, d, e, f, g, h, i, j, k are each independently selected from 0.1 to 10.
In a preferred embodiment, the support is selected from the group consisting of molecular sieves, preferably at least one of the group consisting of a type a molecular sieves, an X type molecular sieves and a Y type molecular sieves, for example a Y type molecular sieve.
In a preferred embodiment, the weight ratio of the metal cyanide complex to the carrier is 1 (0.1 to 1000), preferably 1 (1 to 100), more preferably 1 (2 to 30).
In a preferred embodiment, the supported metal cyanide complex catalyst consists of a catalyst comprising M 1 Metal salt of M 2 Metal cyanide, M 3 Is prepared from the raw materials including metal cyanide, organic ligand Y, organic ligand Z, carrier and shaping agent.
The choice of each raw material is the same as that defined in the preparation method.
Another object of the present application is to provide a method for preparing the supported metal cyanide complex catalyst according to one of the objects of the present application, comprising: and adding the carrier in the process of preparing the metal cyanide complex, and drying and forming to obtain the supported metal cyanide complex catalyst.
In a preferred embodiment, when the metal cyanide complex is selected from the group consisting of the multimetal cyanide complexes of formula (I), the preparation method comprises the steps of:
step 1, M is 1 Metal salt of M 2 Metal cyanide, M 3 Mixing the metal cyanide of (a) with water to form an aqueous solution;
step 2, adding the organic ligand Y and/or the aqueous solution thereof, the organic ligand Z and/or the aqueous solution thereof and the carrier into the aqueous solution, and dispersing to obtain a suspension;
step 3, filtering or centrifuging the suspension to obtain a filter cake;
step 4, dispersing the filter cake by adopting an organic ligand Y and/or an aqueous solution thereof, adding an organic ligand Z and/or an aqueous solution thereof, and filtering or centrifuging after dispersing to obtain a supported catalyst powder;
and 5, drying the supported catalyst powder, adding a forming agent, and sequentially performing adhesion, optional layering, granulating and drying to obtain the supported metal cyanide complex catalyst.
In step 2, the organic ligand Y and/or its aqueous solution, the organic ligand Z and the carrier are not added sequentially, and the organic ligand Y and/or its aqueous solution and the carrier may be added first, and then the organic ligand Z may be added after the reaction.
In a preferred embodiment, the M 1 The metal salt of (2) is water-soluble M 1 Salts, preferably from M 1 At least one of the hydrochloride, sulfate, acetate, bromide, cyanide, thiocyanate and nitrate salts of (c).
In a further preferred embodiment, said M 1 Is selected from at least one of zinc chloride, zinc bromide, zinc acetate, zinc sulfate, manganese chloride and manganese acetate.
In a preferred embodiment, the M 2 Metal cyanide and M of (2) 3 Independently selected from water-soluble metal cyanide salts, preferably from water-soluble potassium cyanide salts.
In a further preferred embodiment, said M 2 Metal cyanide and M of (2) 3 Independently selected from at least one of potassium hexacyanocobaltate, potassium hexacyanoferrate, calcium hexacyanocobaltate and potassium tetracyanonickelate, or a mixture of two or more thereof.
In a still further preferred embodiment, M 2 Metal cyanide and M of (2) 3 Is different from the metal cyanide.
In a preferred embodiment, M 2 Metal cyanide of (2) is selected from K 3 [Co(CN) 6 ]，M 3 Metal cyanide of (2) is selected from K 2 [CoFe(CN) 6 ]Alternatively, M 2 Metal cyanide of (2) is selected from K 2 [CoFe(CN) 6 ]，M 3 Metal cyanide of (2) is selected from K 3 [Co(CN) 6 ]。
In a preferred embodiment, the support is selected from molecular sieves.
In a further preferred embodiment, the molecular sieve is selected from at least one of a type a molecular sieve, an X type molecular sieve, and a Y type molecular sieve, for example a Y type molecular sieve.
In a preferred embodiment, the organic ligand Y is selected from organic alcohols, preferably from C 4 ～C 10 Organic alcohols, more preferably from t-butanolAnd/or t-amyl alcohol.
In a preferred embodiment, the organic ligand Z is selected from at least one of aliphatic esters (e.g. ethyl acetate), aromatic monoesters and aromatic diesters.
In a further preferred embodiment, the organic ligand Z is selected from aromatic diesters, more preferably from phthalates and/or dibutyl phthalate.
In a preferred embodiment, the molding agent is selected from at least one of silica, alumina, polyethylene glycol, polyolefin.
In a preferred embodiment, the M 1 Metal salt of M 2 Metal cyanide, M 3 The weight ratio of the metal cyanide to the organic ligand Y to the organic ligand Z is 1 (0.01-1): 5-100): 0.01-1.5.
In a further preferred embodiment, said M 1 Metal salt of M 2 Metal cyanide, M 3 The weight ratio of the metal cyanide to the organic ligand Y to the organic ligand Z is 1 (0.1-0.8): 0.05-0.6): 8-30): 0.2-1.
In a preferred embodiment, the weight ratio of the metal cyanide complex to the carrier is 1 (0.1 to 1000), preferably 1 (1 to 100), more preferably 1 (2 to 30).
In a preferred embodiment, the weight ratio of the molding agent to the catalyst powder is 1: (0.01-10), preferably (1.5-8).
In the present application, the bonding is performed in a bonder, and the layering and dicing are performed in a layering machine.
In a preferred embodiment, steps 1 to 4 are all carried out with stirring.
In a further preferred embodiment, steps 1 to 4 are stirred at a speed of 4000 to 12000 r/min.
In a still further preferred embodiment, steps 1 to 4 are stirred at a speed of 6000 to 10000 r/min.
In a preferred embodiment, in step 5, the drying is carried out at 80 to 150 ℃, preferably 100 to 140 ℃.
The third object of the present application is to provide a supported metal cyanide complex catalyst obtained by the second object of the present application.
The fourth object of the application is to provide an application of the supported metal cyanide complex catalyst of one of the objects of the application or the supported metal cyanide complex catalyst obtained by the two preparation methods of the object of the application in the preparation of polyether polyol.
The supported metal cyanide complex catalyst can be dispersed in a kettle type reactor and a tubular reactor for application and can also be applied in a fixed bed reactor.
Compared with the prior art, the application has the following beneficial effects: the supported metal cyanide complex catalyst well solves the defects that the metal cyanide complex has higher cost, is not easy to remove and cannot be reused. And can solve the environmental problem of exceeding the standard of the transition metal content caused by the deposition of the metal cyanide complex catalyst in the polyether production device.
Detailed Description
The present application is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present application and should not be construed as limiting the scope of the present application, and some insubstantial modifications and adjustments of the present application by those skilled in the art from the present disclosure are still within the scope of the present application.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
Will be 5.6g K 3 [Co(CN) 6 ]And 2.52g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, followed by the addition of 100mL of t-butanol and 100mL of deionized waterAnd adding 26g of NaY type molecular sieve into the mixed solution of the ionized water, stirring for 25min, adding 14.5g of mixed solution of dimethyl phthalate and 200mL of deionized water into the mixed solution, continuously stirring for 10min, and vacuum-filtering by using a sand core funnel. Finally, the obtained solid was added to a mixture of 150mL of t-butanol and 50mL of deionized water, stirred at a speed of 8000r/min for 10min, then 10.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. 220mL of tertiary butanol is added to the obtained solid, stirring is carried out for 10min at the speed of 8000r/min, 6.8g of dimethyl phthalate is added, stirring is carried out for 10min, centrifugal separation is carried out, and 35g of supported catalyst powder is obtained. To 35g of the obtained supported catalyst powder, 15g of deionized water, 10g of silica and 0.5g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm, and then cut into a cylindrical shape having a length of 3 mm. Vacuum drying at 120deg.C to obtain load MMC-1.
[ example 2 ]
Will be 5.6g K 3 [Co(CN) 6 ]And 2.52g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, then a mixture of 100mL of tertiary butanol and 100mL of deionized water is added, then 120g of NaY type molecular sieve is added, stirring is carried out for 25min, then a mixture of 14.5g of dimethyl phthalate and 200mL of deionized water is added thereto, stirring is continued for 10min, and vacuum filtration is carried out by using a sand core funnel. Finally, the obtained solid was added to a mixture of 150mL of t-butanol and 50mL of deionized water, stirred at a speed of 8000r/min for 10min, then 10.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. 220mL of tertiary butanol is added to the obtained solid, stirring is carried out for 10min at the speed of 8000r/min, 6.8g of dimethyl phthalate is added, stirring is carried out for 10min, centrifugal separation is carried out, and 130g of supported catalyst powder is obtained. To 130g of the obtained supported catalyst powder, 60g of deionized water, 40g of silica and 1g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm, and then cut into a cylindrical shape having a length of 3 mm. At 120Vacuum drying at the temperature of DEG C to obtain the MMC-2.
[ example 3 ]
Will be 5.6g K 3 [Co(CN) 6 ]And 2.52g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, then a mixture of 100mL of tertiary butanol and 100mL of deionized water is added, then 120g of NaY type molecular sieve is added, stirring is carried out for 25min, then a mixture of 14.5g of dimethyl phthalate and 200mL of deionized water is added thereto, stirring is continued for 10min, and vacuum filtration is carried out by using a sand core funnel. Finally, the obtained solid was added to a mixture of 150mL of t-butanol and 50mL of deionized water, stirred at a speed of 8000r/min for 10min, then 10.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. 220mL of tertiary butanol is added to the obtained solid, stirring is carried out for 10min at the speed of 8000r/min, 6.8g of dimethyl phthalate is added, stirring is carried out for 10min, centrifugal separation is carried out, and 132g of supported catalyst powder is obtained. To 132g of the obtained supported catalyst powder, 60g of deionized water, 60g of silica and 1g of polyethylene glycol 2000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm, and then cut into a cylindrical shape having a length of 3 mm. Vacuum drying at 120deg.C to obtain MMC-3.
[ example 4 ]
Will be 2.5g K 3 [Co(CN) 6 ]And 1.25g K 2 [CoFe(CN) 6 ]To 150mL of deionized water was added to dissolve the solution, then 65g of a 38.5% (by weight) aqueous solution of manganese chloride was added thereto at a rotational speed of 8000r/min, followed by a mixture of 53.3mL of t-amyl alcohol and 55mL of deionized water, then 15.6g of NaY-type molecular sieve was added thereto, and after stirring for 25min, a mixture of 2.27g of dioctyl phthalate and 20mL of deionized water was added thereto, and after continuing stirring for 10min, vacuum filtration was performed with a sand core funnel. Finally, the obtained solid was added to a mixture of 79.5mL of t-amyl alcohol and 30mL of deionized water, stirred at a speed of 8000r/min for 10min, then 1.67g of dioctyl phthalate was added, stirred for 10min, and then centrifuged. The resulting solid was added again 116.3mL of t-amyl alcohol is stirred for 10min at a speed of 8000r/min, 1.1g of dioctyl phthalate is added, and after stirring for 10min, centrifugal separation and drying are carried out to obtain 23.5g of supported catalyst powder. To 23.5g of the obtained supported catalyst powder, 5g of deionized water, 2.5g of silica and 0.5g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm and then cut into a cylinder of 3mm in length. Vacuum drying at 120deg.C to obtain load MMC-4.
[ example 5 ]
Will be 12.5g K 3 [Co(CN) 6 ]And 7.5g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, then a mixture of 137mL of tertiary butanol and 140mL of deionized water was added, then 183g of NaY-type molecular sieve was added, and after stirring for 25min, a mixture of 9.1g of dimethyl phthalate and 50mL of deionized water was added thereto, and after continuing stirring for 10min, vacuum filtration was performed using a sand core funnel. Finally, the obtained solid was added to a mixture of 205mL of t-butanol and 80mL of deionized water, stirred at a speed of 8000r/min for 10min, then 6.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. The obtained solid was further added with 300mL of t-butanol, stirred at 8000r/min for 10min, then added with 4.3g of dimethyl phthalate, stirred for 10min, and then centrifugally separated and dried to obtain 195g of supported catalyst powder. To 195g of the obtained supported catalyst powder, 30g of deionized water, 35g of silica, 4g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm, and then cut into a cylindrical shape having a length of 3 mm. Vacuum drying at 120deg.C to obtain load MMC-5.
[ example 6 ]
Will be 20g K 3 [Co(CN) 6 ]And 15g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, followed by addition of a mixture of 205mL of t-butanol and 200mL of deionized water, followed by 489g of NaY typeMolecular sieve, stirring for 25min, adding 11.4g of mixed solution of dimethyl phthalate and 100mL of deionized water, stirring for 10min, and vacuum filtering with a sand core funnel. Finally, the obtained solid was added to a mixture of 308mL of t-butanol and 100mL of deionized water, stirred at a speed of 8000r/min for 10min, then 8.3g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. The obtained solid was further added with 454mL of t-butanol, stirred at 8000r/min for 10min, then 5.3g of dimethyl phthalate was added, stirred for 10min, and then centrifuged and dried to obtain 505g of supported catalyst powder. To 505g of the obtained supported catalyst powder, 200g of deionized water, 300g of silica and 35g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and the mixture was bar-pressed in a plodder to a diameter of 2mm, and then cut into a cylindrical shape having a length of 3 mm. Vacuum drying at 120deg.C to obtain load MMC-6.
[ example 7 ]
Adding 40g of polyoxypropylene propanediol with a hydroxyl value of about 280.0mgKOH/g and 0.5g of supported catalyst MMC-1 into a 1L pressure-resistant reactor, vacuumizing and heating to more than 120 ℃, slowly adding 360g of propylene oxide, maintaining the pressure of the reactor to be not more than 0.15MPa, when the pressure of the reactor becomes negative pressure and is not reduced any more, indicating that the reaction is finished, cooling and discharging 398.2g of polyether glycol containing the supported catalyst, wherein the total reaction time is 40 minutes. The hydroxyl value was 27.6mgKOH/g, the unsaturation degree was 0.008mmol/g, and the molecular weight distribution was 1.06.
[ example 8 ]
The catalyst MMC-1 in the polyether discharged in example 7 was filtered out, and was again added to a reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added, and example 7 was repeated to obtain 398g of polyether glycol having a hydroxyl value of 28.0mgKOH/g, an unsaturation degree of 0.009mmol/g, and a molecular weight distribution of 1.06.
[ example 9 ]
The catalyst MMC-1 in the polyether discharged in example 8 was filtered out, and was again added to a reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added, and example 8 was repeated to obtain 397g of polyether diol having a hydroxyl value of 28.1mgKOH/g, an unsaturation degree of 0.009mmol/g, and a molecular weight distribution of 1.07.
[ example 10 ]
As in example 7, except that 0.5g of MMC-1 was changed to 1g of MMC-2, 399g of polyether diol was obtained, the hydroxyl value was 27.4mgKOH/g, the unsaturation degree was 0.008mmol/g, and the molecular weight distribution was 1.05.
[ example 11 ]
The catalyst MMC-2 of the polyether discharged in example 10 was filtered out, and was again added to a reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added, and example 10 was repeated except that MMC-1 was changed to MMC-2, to obtain 398g of polyether glycol having a hydroxyl value of 28.3mgKOH/g, an unsaturation degree of 0.008mmol/g, and a molecular weight distribution of 1.06.
[ example 12 ]
As in example 7, except that 0.5g of MMC-1 was changed to 1g of MMC-3, 399g of polyether diol was obtained, the hydroxyl value was 27.5mgKOH/g, the unsaturation degree was 0.009mmol/g, and the molecular weight distribution was 1.06.
[ example 13 ]
The catalyst MMC-3 of the polyether discharged in example 12 was filtered out, and was again added to a reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added, and example 12 was repeated except that MMC-1 was changed to MMC-3, to obtain 398g of polyether glycol having a hydroxyl value of 28.4mgKOH/g, an unsaturation degree of 0.009mmol/g, and a molecular weight distribution of 1.06.
[ example 14 ]
Adding about 50g of polyoxypropylene glycerol with a hydroxyl value of 336.0mgKOH/g and 0.5g of catalyst MMC-1 into a 1L pressure-resistant reactor, vacuumizing and heating to more than 120 ℃, slowly adding 250g of propylene oxide, maintaining the pressure of the reactor to be not more than 0.15MPa, when the pressure of the reactor becomes negative pressure and is not reduced, indicating that the reaction is finished, wherein the total reaction time is 30 minutes, and cooling to obtain 298.0g of polyether triol. The hydroxyl number was 55.5mgKOH/g, the unsaturation degree was 0.008mmol/g, and the molecular weight distribution was 1.09.
[ example 15 ]
The catalyst MMC-1 in the polyether discharged in example 14 was filtered out, and was again added to a reaction vessel, and similarly, 50g of polyoxypropylene glycerol having a hydroxyl value of about 336.0mgKOH/g was added, and example 14 was repeated to obtain 297g of polyether glycol having a hydroxyl value of 56.0mgKOH/g, an unsaturation degree of 0.009mmol/g, and a molecular weight distribution of 1.09.
[ example 16 ]
The catalyst MMC-1 in the polyether discharged in example 15 was filtered out, and was again added to a reaction vessel, and similarly, 50g of polyoxypropylene glycerol having a hydroxyl value of about 336.0mgKOH/g was added, and example 15 was repeated to obtain 297g of polyether triol having a hydroxyl value of 56.2mgKOH/g, a degree of unsaturation of 0.009mmol/g, and a molecular weight distribution of 1.09.
Comparative example 1
Will be 5.6g K 3 [Co(CN) 6 ]And 2.52g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, then a mixture of 100mL of tertiary butanol and 100mL of deionized water was added, then 26g of ethyl orthosilicate was added, and after stirring for 25min, a mixture of 14.5g of dimethyl phthalate and 200mL of deionized water was added thereto, and after continuing stirring for 10min, vacuum filtration was performed with a sand core funnel. Finally, the obtained solid was added to a mixture of 150mL of t-butanol and 50mL of deionized water, stirred at a speed of 8000r/min for 10min, then 10.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. 220mL of t-butanol was added to the obtained solid, and after stirring at 8000r/min for 10min, 6.8g of dimethyl phthalate was added, and after stirring for 10min, centrifugal separation and drying were performed to obtain 30g of white solid Cat-1.
40g of polyoxypropylene propanediol with a hydroxyl value of about 280.0mgKOH/g and 0.5g Cat-1 are added into a 1L pressure-resistant reactor, the temperature is raised to above 120 ℃ by vacuum pumping, 360g of propylene oxide is slowly added, the pressure of the reactor is maintained to be not more than 0.15MPa, when the pressure of the reactor becomes negative pressure and is not reduced any more, the reaction is finished, the total reaction time is 40 minutes, and 399.0g of polyether glycol containing a supported catalyst is cooled and discharged. The hydroxyl value was 27.6mgKOH/g, the unsaturation degree was 0.009mmol/g, and the molecular weight distribution was 1.07.
Filtering Cat-1 in the product, adding the filtered Cat-1 into a reaction kettle again, adding 40g of polyoxypropylene propanediol with the hydroxyl value of about 280.0mgKOH/g, repeating the polymerization, adding 20g of propylene oxide, and stirring for 2 hours, wherein the pressure does not drop, and the repeated use of the Cat-1 is proved to be inactive.
Comparative example 2
Will be 5.6g K 3 [Co(CN) 6 ]And 2.52g K 2 [CoFe(CN) 6 ]Dissolving in 150mL of deionized water, and adding 38.5 wt.% ZnCl at 8000r/min 2 65g of aqueous solution, then a mixture of 100mL of tertiary butanol and 100mL of deionized water was added, then 26g of ethyl titanate was added, and after stirring for 25min, a mixture of 14.5g of dimethyl phthalate and 200mL of deionized water was added thereto, and after continuing stirring for 10min, vacuum filtration was performed with a sand core funnel. Finally, the obtained solid was added to a mixture of 150mL of t-butanol and 50mL of deionized water, stirred at a speed of 8000r/min for 10min, then 10.6g of dimethyl phthalate was added, stirred for 10min, and then centrifuged. 220mL of t-butanol was added to the obtained solid, and after stirring at 8000r/min for 10min, 6.8g of dimethyl phthalate was added, and after stirring for 10min, centrifugal separation and drying were performed to obtain 33g of white solid Cat-2.
40g of polyoxypropylene propanediol with a hydroxyl value of about 280.0mgKOH/g and 0.5g Cat-2 are added into a 1L pressure-resistant reactor, the temperature is raised to above 120 ℃ by vacuum pumping, 360g of propylene oxide is slowly added, the pressure of the reactor is maintained to be not more than 0.15MPa, when the pressure of the reactor becomes negative pressure and is not reduced any more, the reaction is finished, the total reaction time is 40 minutes, and 397.0g of polyether glycol containing a supported catalyst is cooled and discharged. The hydroxyl value was 27.3mgKOH/g, the unsaturation degree was 0.008mmol/g, and the molecular weight distribution was 1.08.
Filtering Cat-1 in the product, adding the filtered Cat-1 into a reaction kettle again, adding 40g of polyoxypropylene propanediol with the hydroxyl value of about 280.0mgKOH/g, repeating the polymerization, adding 20g of propylene oxide, stirring for 2 hours, and ensuring that the pressure does not drop, thus proving that the Cat-2 is inactive for repeated use.
As is clear from the comparison of comparative examples 1 to 2 with examples, the catalyst cannot be reused by using silica and titania as carriers, probably because silica and titania have no suitable pore channels and have weak adsorption force on the metal cyanide complex catalyst; the application adopts molecular sieve, which has unique pore canal and adsorption property, and can adsorb metal ions into the pore canal of the molecular sieve or make the metal ions enter the framework of the molecular sieve after contacting with the metal ions, thus obtaining the catalyst with specific catalytic effect (unexpected).
Therefore, the supported metal cyanide complex catalyst prepared by the molecular sieve can be filtered out for repeated use, and the defects that the existing metal cyanide complex is high in cost, difficult to remove and incapable of being reused are overcome. And can solve the environmental problem of exceeding the standard of the transition metal content caused by the deposition of the metal cyanide complex catalyst in the polyether production device.
Claims (22)
1. A supported metal cyanide complex catalyst comprising a support and a metal cyanide complex supported on the support, wherein the metal cyanide complex is selected from the group consisting of multimetal cyanide complexes and the support is selected from the group consisting of molecular sieves;
the multimetal cyanide complex has the general formula shown in formula (I):
M 1 a [M 2 d (CN) f ]. M 1 b [M 3 e (CN) g ]. M 1 c X h . Y i . Z j . kH 2 o is of formula (I);
wherein, in formula (I):
M 1 selecting Zn, ni or Co;
M 3 selected from Zn or Fe;
M 2 selected from Fe or Co;
x is selected from halogen element, CN - 、SCN - 、NO 3 - 、CO 3 2- 、SO 4 2- Or ClO 3 2- ；
Y is selected from tertiary butanol or tertiary amyl alcohol;
z is selected from aromatic diesters;
a. b, c, d, e, f, g, h, i, j, k are each independently selected from 0.1 to 10.
2. The supported metal cyanide complex catalyst of claim 1, wherein Z is phthalate and/or dibutyl phthalate.
3. The supported metal cyanide complex catalyst of any one of claims 1-2, wherein the support is selected from at least one of a type a molecular sieve, an X type molecular sieve, and a Y type molecular sieve.
4. The supported metal cyanide complex catalyst of claim 3, wherein the weight ratio of the metal cyanide complex to the support is 1 (0.1-1000).
5. The supported metal cyanide complex catalyst of claim 4, wherein the weight ratio of the metal cyanide complex to the support is 1 (1-100).
6. A process for preparing a supported metal cyanide complex catalyst as claimed in any one of claims 1 to 5, comprising: and adding the carrier in the process of preparing the metal cyanide complex, and drying and forming to obtain the supported metal cyanide complex catalyst.
7. The process according to claim 6, wherein the metal cyanide complex is selected from the group consisting of multimetal cyanide complexes of the formula (I), comprising the steps of:
step 1, M is 1 Metal salt of M 2 Metal cyanide, M 3 Is mixed with water to formAn aqueous solution;
step 2, adding the organic ligand Y and/or the aqueous solution thereof, the organic ligand Z and/or the aqueous solution thereof and the carrier into the aqueous solution, and dispersing to obtain a suspension;
step 3, filtering or centrifuging the suspension to obtain a filter cake;
step 4, dispersing the filter cake by adopting an organic ligand Y and/or an aqueous solution thereof, adding an organic ligand Z and/or an aqueous solution thereof, and filtering or centrifuging after dispersing, and optionally repeating the step to obtain a supported catalyst powder;
and 5, drying the supported catalyst powder, adding a forming agent, and sequentially performing adhesion, optional layering, granulating and drying to obtain the supported metal cyanide complex catalyst.
8. The method of claim 7, wherein M is 1 The metal salt of (2) is water-soluble M 1 And (3) salt.
9. The method of claim 8, wherein M is 1 Is selected from the group consisting of M 1 At least one of the hydrochloride, sulfate, acetate, bromide, cyanide, thiocyanate and nitrate salts of (c).
10. The method of claim 9, wherein M is 1 Is selected from at least one of zinc chloride, zinc bromide, zinc acetate, zinc sulfate, manganese chloride and manganese acetate.
11. The method of claim 7, wherein M is 2 Metal cyanide and M of (2) 3 Independently selected from water-soluble cyanide metallates.
12. The method of claim 11, wherein M is 2 Metal cyanide and M of (2) 3 Independently selected from the group consisting of water-soluble metal cyanide compoundsPotassium metal cyanide.
13. The method of claim 11, wherein M is 2 Metal cyanide and M of (2) 3 Independently selected from at least one of potassium hexacyanocobaltate, potassium hexacyanoferrate, calcium hexacyanocobaltate and potassium tetracyanonickelate, or a mixture of two or more thereof.
14. The method according to claim 7, wherein,
the carrier is selected from molecular sieves; and/or
The forming agent is at least one selected from silicon dioxide, aluminum oxide, polyethylene glycol and polyolefin.
15. The method of claim 14, wherein the process comprises,
the carrier is selected from at least one of A-type molecular sieve, X-type molecular sieve and Y-type molecular sieve.
16. The method according to claim 7, wherein,
the organic ligand Y is selected from tertiary butanol and/or tertiary amyl alcohol; and/or
The organic ligand Z is selected from aromatic diesters.
17. The method of claim 16, wherein the process comprises,
the organic ligand Z is selected from phthalate and/or dibutyl phthalate.
18. The method according to any one of claim 7 to 17, wherein,
the M is 1 Metal salt of M 2 Metal cyanide, M 3 The weight ratio of the metal cyanide to the organic ligand Y to the organic ligand Z is 1 (0.01-1): 5-100): 0.01-1; and/or
The weight ratio of the metal cyanide complex to the carrier is 1 (0.1-1000); and/or
The weight ratio of the molding agent to the catalyst powder is 1: (0.01-10).
19. The method of claim 18, wherein the process comprises,
the weight ratio of the metal cyanide complex to the carrier is 1 (1-100).
20. The method of claim 18, wherein the process comprises,
the bonding is performed in a bonding machine, and the layering and the granulating are performed in the layering machine; and/or
The steps 1-4 are all carried out under stirring.
21. A supported metal cyanide complex catalyst obtainable by the process of any one of claims 6 to 20.
22. Use of a supported metal cyanide complex catalyst according to one of claims 1 to 5 or a supported metal cyanide complex catalyst obtainable by a process according to one of claims 6 to 20 for the preparation of polyether polyols.
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