Supported metal cyanide complex catalyst and preparation method and application thereof
阅读说明：本技术 一种负载型金属氰化络合物催化剂及其制备方法和应用 (Supported metal cyanide complex catalyst and preparation method and application thereof ) 是由 宰少波 金晖 张志华 于 2020-07-01 设计创作，主要内容包括：本发明公开了一种负载型金属氰化络合物催化剂及其制备方法和应用,所述催化剂包括载体和负载于所述载体上的金属氰化络合物,其中,所述金属氰化络合物选自双金属氰化络合物和/或多金属氰化络合物,所述载体选自分子筛,所述金属氰化络合物与所述载体的重量比为1:(0.1～1000),优选1:(1～100)。所述制备方法包括：在制备所述金属氰化络合物的过程中加入所述载体,经烘干、成型得到所述负载型金属氰化络合物催化剂。本发明所述负载型金属氰化络合物催化剂较好地解决了金属氰化络合物成本较高,不易脱除,不能重复使用的缺点。并且可以解决聚醚生产装置中,金属氰化络合物催化剂沉积,造成过渡金属含量超标的环境问题。(The invention 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 loaded on the carrier, wherein the metal cyanide complex is selected from a bimetallic cyanide complex and/or a polymetallic cyanide complex, the carrier is selected from a 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, drying and molding to obtain the supported metal cyanide complex catalyst. The supported metal cyanide complex catalyst of the invention better solves the defects of high cost, difficult removal and incapability of being reused of the metal cyanide complex. And the environmental problem that the content of transition metal exceeds the standard due to the deposition of a metal cyanide complex catalyst in a polyether production device can be solved.)
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 a bimetallic cyanide complex and/or a multimetallic cyanide complex.
2. The supported metal cyanide complex catalyst of claim 1, wherein the multimetallic cyanide complex has the general formula shown in formula (I):
M1 a[M2 d(CN)f].M1 b[M3 e(CN)g].M1 cXh.Yi.Zj.kH2o is formula (I);
wherein, in formula (I):
M1、M3independently selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr, M2Selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, and M1、M2And M3Are different from each other; and/or
X is selected from halogen element and CN-、SCN-、NO3 -、CO3 2-、SO4 2-Or ClO3 2-(ii) a And/or
Y is selected from organic alcohols, preferably from C4～C10An organic alcohol; and/or
Z is selected from aliphatic ester, aromatic monoester or aromatic diester; and/or
a. b, c, d, e, f, g, h, i, j and k are respectively and independently selected from 0.1-20.
3. The supported metal cyanide complex catalyst of claim 2, characterized in that in formula (I):
M1preferably Zn, Ni or Co; and/or
M3Selected from Zn or Fe; and/or
M2Selected 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 phthalates and/or dibutylphthalates; and/or
a. b, c, d, e, f, g, h, i, j and k are independently selected from 0.1-10.
4. The supported metal cyanide complex catalyst of any of claims 1 to 3, wherein the support is selected from molecular sieves, preferably at least one of type A molecular sieves, type X molecular sieves and type Y molecular sieves.
5. The supported metal cyanide complex catalyst according to claim 4, characterized in that the weight ratio of the metal cyanide complex to the support is 1 (0.1-1000), preferably 1 (1-100).
6. A method for preparing the supported metal cyanide complex catalyst of any one of claims 1 to 5, comprising: and adding the carrier in the process of preparing the metal cyanide complex, drying and molding to obtain the supported metal cyanide complex catalyst.
7. The method of claim 6, wherein when the metal cyanide complex is selected from the group consisting of polymetallic cyanide complexes of formula (I), the method comprises the steps of:
step 1, adding M1Metal salt of (2), M2Metal cyanide compounds of (2), M3Mixing the metal cyanide compound 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, filtering or centrifuging after dispersing, and optionally repeating the step to obtain supported catalyst powder;
and 5, drying the supported catalyst powder, adding a forming agent, and sequentially performing adhesion, optional pressing and particle cutting, and drying to obtain the supported metal cyanide complex catalyst.
8. The method of claim 7, wherein M is1The metal salt of (A) is water-soluble M1Salts, preferably from M1At least one of a hydrochloride, a sulfate, an acetate, a bromide, a cyanide, a thiocyanide and a nitrate, more preferably at least one selected from the group consisting of zinc chloride, zinc bromide, zinc acetate, zinc sulfate, manganese chloride and manganese acetate.
9. The method of claim 7, wherein M is2Metal cyanide compounds of (2) and M3The metal cyanide of (a) is independently selected from water soluble cyanide metalates, preferably from water soluble cyanide metalates of potassium, more preferably from at least one or a mixture of two or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium hexacyanocobaltate, calcium hexacyanocobaltate and potassium tetracyanonickelate.
10. The production method according to claim 7,
the carrier is selected from molecular sieves, preferably at least one of A-type molecular sieves, X-type molecular sieves and Y-type molecular sieves; and/or
The forming agent is at least one of silicon dioxide, aluminum oxide, polyethylene glycol and polyolefin.
11. The production method according to claim 7,
the organic ligand Y is selected from organic alcohols, more preferably from C4～C10Organic alcohols, more preferably from tert-butanol and/or tert-amyl alcohol; and/or
The organic ligand Z is selected from at least one of aliphatic ester, aromatic monoester and aromatic diester, preferably from aromatic diester, more preferably from phthalate and/or dibutyl phthalate.
12. The production method according to any one of claims 7 to 11,
the M is1Metal salt of (2), M2Metal cyanide compounds of (2), M3The weight ratio of the metal cyanide, the organic ligand Y and 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), preferably 1 (1-100); and/or
The weight ratio of the forming agent to the catalyst powder is 1: (0.01-10).
13. The production method according to claim 12,
the bonding is carried out in a bonding machine, and the layering and the grain cutting are carried out in a plodder; and/or
The steps 1 to 4 are all carried out under stirring, and the stirring is preferably carried out at the speed of 4000 to 12000 r/min.
14. A supported metal cyanide complex catalyst obtained by the production method according to any one of claims 6 to 13.
15. Use of the supported metal cyanide complex catalyst according to any one of claims 1 to 5 or the supported metal cyanide complex catalyst obtained by the production method according to any one of claims 6 to 13 for producing polyether polyols.
Technical Field
The present invention is in the field of metal catalysts, particularly to supported multimetallic catalysts, and in particular to supported metal cyanide complex catalysts for the preparation of polyether polyols.
Background
Polyether polyol is a substance containing two or more hydroxyl groups (-OH) in a molecule and an ether group, can react with polyisocyanate to prepare polyurethane, and has wide application. Polyether polyols are typically prepared by ring-opening polymerization of epoxy monomers using an alkali metal hydroxide (e.g., KOH) as a catalyst. However, KOH causes an isomerization side reaction of the epoxy compound, thereby increasing the content of the monool having a double bond other than a hydroxyl group at the terminal of the polyol.
Since the preparation of polyether polyols by the american general tire rubber company of the sixties of the last century, the bimetallic catalysts have a great number of literature reports, such as documents US3427256, US3427334, US5158922, US5470813, US5482908, US5627120, EP6755716, CN1221561C, etc.
The bimetallic catalyst activity is far in excess of KOH and the resulting polyether polyols have very low unsaturation. However, an induction period with a certain period of time is generally present, and a phenomenon of excessively rapid temperature rise occurs at the reaction initiation stage. Our prior patent application CN101302286A discloses a multi-metal (MMC) catalyst, which solves the problems of long induction period and difficult control of reaction temperature.
However, DMC is relatively expensive, difficult to remove, and not reusable, and in industrial polymerizers, because of long-term accumulation of DMC catalysts, environmental problems such as excessive transition metals can be caused.
The invention is based on an MMC catalyst which is independently researched and developed, and the MMC catalyst is loaded on a molecular sieve to prepare the loaded MMC catalyst. The catalyst has high activity, can be repeatedly used, is convenient to remove, and better solves the problems.
Disclosure of Invention
In order to solve the problems of high cost, difficult removal and incapability of repeated use of the MMC in the prior art, the invention provides a supported multi-metal catalyst, and can solve the environmental problem that the content of transition metal exceeds the standard due to deposition of the MMC catalyst in a polyether production device.
One of the objects of the present invention is 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 a double metal cyanide complex (DMC) and/or a multiple metal cyanide complex.
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):
M1 a[M2 d(CN)f].M1 b[M3 e(CN)g].M1 cXh.Yi.Zj.kH2o is formula (I);
wherein, in formula (I):
M1、M3independently selected from Zn, Fe, Ni, Mn, Co, Sn, Ph, Mo, Al, V, Sr, W, Cu or Cr, M2Selected from Fe, Co, Cr, Mn, Ir, Ni, Rh, Ru or V, and M1、M2And M3Are different from each other; and/or
X is selected from halogen element and CN-、SCN-、NO3 -、CO3 2-、SO4 2-Or ClO3 2-(ii) a And/or
Y is selected from organic alcohols, preferably from C4～C10An organic alcohol; and/or
Z is selected from aliphatic ester, aromatic monoester or aromatic diester; and/or
a. b, c, d, e, f, g, h, i, j and k are respectively and independently selected from 0.1-20.
Wherein a, b and c represent M1D and e represent M2、M3F and g represent the ion number of CN, H, i, j and k represent X, Y, Z and H, respectively2The number of O.
In a further preferred embodiment, in formula (I):
M1preferably Zn, Ni or Co; and/or
M3Selected from Zn or Fe; and/or
M2Selected 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 phthalates and/or dibutylphthalates; and/or
a. b, c, d, e, f, g, h, i, j and k are independently selected from 0.1-10.
In a preferred embodiment, the support is selected from molecular sieves, preferably at least one selected from the group consisting of type a molecular sieves, type X molecular sieves and type Y molecular sieves, such as type Y molecular sieves.
In a preferred embodiment, the weight ratio of the metal cyanide complex to the support 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 M1Metal salt of (2), M2Metal cyanide compounds of (2), M3The metal cyanide, the organic ligand Y, the organic ligand Z, the carrier and the forming agent.
The selection of each raw material is the same as the limitation in the preparation method.
The second object of the present invention is to provide a method for preparing the supported metal cyanide complex catalyst, which comprises: and adding the carrier in the process of preparing the metal cyanide complex, drying and molding to obtain the supported metal cyanide complex catalyst.
In a preferred embodiment, when the metal cyanide complex is selected from multimetal cyanide complexes of the formula (I), the preparation process comprises the following steps:
step 1, adding M1Metal salt of (2), M2Metal cyanide compounds of (2), M3Mixing the metal cyanide compound 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;
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 supported catalyst powder;
and 5, drying the supported catalyst powder, adding a forming agent, and sequentially performing adhesion, optional pressing and particle cutting, 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 in sequence, and the organic ligand Y and/or its aqueous solution and the carrier may be added first, and the organic ligand Z may be added after the reaction.
In a preferred embodiment, said M1The metal salt of (A) is water-soluble M1Salts, preferably from M1At least one of a hydrochloride, a sulfate, an acetate, a bromide, a cyanide, a thiocyanate, and a nitrate.
In a further preferred embodiment, said M1The metal salt of (a) is selected from at least one of zinc chloride, zinc bromide, zinc acetate, zinc sulfate, manganese chloride and manganese acetate.
In a preferred embodiment, said M2Metal cyanide compounds of (2) and M3The metal cyanide of (a) is independently selected from water soluble cyanide metalates, preferably from water soluble potassium cyanide metalates.
In a further preferred embodiment, said M2Metal cyanide compounds of (2) and M3The metal cyanide of (a) is independently selected from at least one or a mixture of two or more of potassium hexacyanocobaltate, potassium hexacyanoferrate, potassium hexacyanocobaltate, calcium hexacyanocobaltate and potassium tetracyanonickelate.
In a still further preferred embodiment, M2Metal cyanide compounds of (2) and M3The metal cyanide compounds of (a) are not identical.
In a preferred embodiment, M2The metal cyanide of (A) is selected from K3[Co(CN)6]，M3Gold (II) ofWith cyanide being selected from K2[CoFe(CN)6]Or, M2The metal cyanide of (A) is selected from K2[CoFe(CN)6]，M3The metal cyanide of (A) is selected from K3[Co(CN)6]。
In a preferred embodiment, the carrier is selected from molecular sieves.
In a further preferred embodiment, the molecular sieve is selected from at least one of type a molecular sieves, type X molecular sieves and type Y molecular sieves, such as type Y molecular sieves.
In a preferred embodiment, the organic ligand Y is selected from organic alcohols, preferably from C4～C10The organic alcohol is more preferably selected from t-butanol and/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 phthalic acid esters and/or dibutyl phthalate.
In a preferred embodiment, the forming agent is selected from at least one of silica, alumina, polyethylene glycol, and polyolefin.
In a preferred embodiment, said M1Metal salt of (2), M2Metal cyanide compounds of (2), M3The weight ratio of the metal cyanide, the organic ligand Y and the organic ligand Z is 1 (0.01-1): 5-100): 0.01-1.5).
In a further preferred embodiment, said M1Metal salt of (2), M2Metal cyanide compounds of (2), M3The weight ratio of the metal cyanide, the organic ligand Y and 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 support 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 forming agent to the catalyst powder is 1: (0.01-10), preferably 1 (1.5-8).
In the present invention, the bonding is performed in a bonder, and the layering and dicing are performed in a plodder.
In a preferred embodiment, steps 1 to 4 are all carried out under stirring.
In a further preferred embodiment, the stirring in step 1-4 is carried out at a speed of 4000-12000 r/min.
In a further preferred embodiment, the step 1-4 is carried out at a speed of 6000-10000 r/min.
In a preferred embodiment, in step 5, the drying is performed at 80 to 150 ℃, preferably 100 to 140 ℃.
The third object of the present invention is to provide a supported metal cyanide complex catalyst obtained by the second object of the present invention.
The fourth object of the present invention is to provide an application of the supported metal cyanide complex catalyst of the first object of the present invention or the supported metal cyanide complex catalyst obtained by the preparation method of the second object of the present invention in the preparation of polyether polyol.
The supported metal cyanide complex catalyst can be dispersed in a tank reactor or a tubular reactor and can also be applied in a fixed bed reactor.
Compared with the prior art, the invention has the following beneficial effects: the supported metal cyanide complex catalyst of the invention better solves the defects of high cost, difficult removal and incapability of being reused of the metal cyanide complex. And the environmental problem that the content of transition metal exceeds the standard due to the deposition of a metal cyanide complex catalyst in a polyether production device can be solved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
5.6g K3[Co(CN)6]And 2.52g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of aqueous solution, then adding a mixed solution of 100mL of tert-butyl alcohol and 100mL of deionized water, then adding 26g of NaY type molecular sieve, stirring for 25min, then adding a mixed solution of 14.5g of dimethyl phthalate and 200mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. And finally, adding the obtained solid into a mixed solution of 150mL of tert-butyl alcohol and 50mL of deionized water, stirring at the speed of 8000r/min for 10min, adding 10.6g of dimethyl phthalate, stirring for 10min, and performing centrifugal separation. And adding 220mL of tert-butyl alcohol into the obtained solid, stirring for 10min at the speed of 8000r/min, adding 6.8g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 35g of supported catalyst powder. 15g of deionized water, 10g of silicon dioxide and 0.5g of polyethylene glycol 6000 are added into 35g of the obtained supported catalyst powder, the mixture is fully mixed in a bonder, and is pressed into a bar in a bar press machine, the diameter of the bar press is 2mm, and then the bar press is cut into a cylinder with the length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain the loaded MMC-1.
[ example 2 ]
5.6g K3[Co(CN)6]And 2.52g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of aqueous solution, then adding a mixed solution of 100mL of tert-butyl alcohol and 100mL of deionized water, then adding 120g of NaY type molecular sieve, stirring for 25min, and then adding 14.5g of dimethyl phthalate and 200mL of deionized waterStirring the mixed solution for 10min, and vacuum-filtering with a sand core funnel. And finally, adding the obtained solid into a mixed solution of 150mL of tert-butyl alcohol and 50mL of deionized water, stirring at the speed of 8000r/min for 10min, adding 10.6g of dimethyl phthalate, stirring for 10min, and performing centrifugal separation. And adding 220mL of tert-butyl alcohol into the obtained solid, stirring at the speed of 8000r/min for 10min, adding 6.8g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 130g of supported catalyst powder. 60g of deionized water, 40g of silicon dioxide and 1g of polyethylene glycol 6000 are added into 130g of the obtained supported catalyst powder, the mixture is fully mixed in a bonder, and is pressed into a bar in a bar press machine, the diameter of the bar press is 2mm, and then the bar press is cut into a cylinder with the length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain MMC-2.
[ example 3 ]
5.6g K3[Co(CN)6]And 2.52g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of aqueous solution, then adding a mixed solution of 100mL of tert-butyl alcohol and 100mL of deionized water, then adding 120g of NaY type molecular sieve, stirring for 25min, then adding a mixed solution of 14.5g of dimethyl phthalate and 200mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. And finally, adding the obtained solid into a mixed solution of 150mL of tert-butyl alcohol and 50mL of deionized water, stirring at the speed of 8000r/min for 10min, adding 10.6g of dimethyl phthalate, stirring for 10min, and performing centrifugal separation. And adding 220mL of tert-butyl alcohol into the obtained solid, stirring at the speed of 8000r/min for 10min, adding 6.8g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 132g of supported catalyst powder. 60g of deionized water, 60g of silicon dioxide and 1g of polyethylene glycol 2000 are added into 132g of the obtained supported catalyst powder, the mixture is fully mixed in a bonder, and is pressed into strips in a plodder with the diameter of 2mm, and then the strips are cut into cylinders with the length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain MMC-3.
[ example 4 ]
2.5g K3[Co(CN)6]And 1.25g K2[CoFe(CN)6]Adding into 150mL deionized water to dissolve, adding into 38.5% (by weight) manganese chloride aqueous solution 65g at 8000r/min, adding mixed solution of 53.3mL tertiary amyl alcohol and 55mL deionized water, adding 15.6g NaY type molecular sieve, stirring for 25min, adding into mixed solution of 2.27g dioctyl phthalate and 20mL deionized water, stirring for 10min, and vacuum filtering with a sand core funnel. Finally, the obtained solid is added into a mixed solution of 79.5mL of tertiary amyl alcohol and 30mL of deionized water, stirred for 10min at the speed of 8000r/min, added with 1.67g of dioctyl phthalate, stirred for 10min and then centrifugally separated. And adding 116.3mL of tert-amyl alcohol into the obtained solid, stirring for 10min at the rotation speed of 8000r/min, adding 1.1g of dioctyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 23.5g of supported catalyst powder. 5g of deionized water, 2.5g of silicon dioxide and 0.5g of polyethylene glycol 6000 are added into 23.5g of the obtained supported catalyst powder, the mixture is fully mixed in a bonder, and is pressed into a bar in a bar press machine, the diameter of the bar press is 2mm, and then the bar press machine is cut into a cylinder with the length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain the loaded MMC-4.
[ example 5 ]
12.5g K3[Co(CN)6]And 7.5g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of aqueous solution, then adding a mixed solution of 137mL of tert-butyl alcohol and 140mL of deionized water, then adding 183g of NaY type molecular sieve, stirring for 25min, then adding a mixed solution of 9.1g of dimethyl phthalate and 50mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. Finally, the obtained solid is added into a mixed solution of 205mL of tert-butyl alcohol and 80mL of deionized water, stirred for 10min at the speed of 8000r/min, added with 6.6g of dimethyl phthalate, stirred for 10min and then centrifugally separated. Adding 300mL of tert-butyl alcohol into the obtained solid, stirring at 8000r/min for 10min, adding 4.3g of dimethyl phthalate, stirring for 10min, centrifuging, and drying to obtain the final productTo 195g of supported catalyst powder. To 195g of the obtained supported catalyst powder, 30g of deionized water, 35g of silicon dioxide and 4g of polyethylene glycol 6000 were added, and the mixture was thoroughly mixed in a bonder, and was plodded in a plodder to have a diameter of 2mm, and then cut into cylinders having a length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain the loaded MMC-5.
[ example 6 ]
20g K3[Co(CN)6]And 15g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of the aqueous solution, then adding a mixed solution of 205mL of tert-butyl alcohol and 200mL of deionized water, then adding 489g of NaY type molecular sieve, stirring for 25min, then adding a mixed solution of 11.4g of dimethyl phthalate and 100mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. And finally, adding the obtained solid into a mixed solution of 308mL of tert-butyl alcohol and 100mL of deionized water, stirring at the speed of 8000r/min for 10min, adding 8.3g of dimethyl phthalate, stirring for 10min, and performing centrifugal separation. And adding 454mL of tertiary butanol into the obtained solid, stirring at the speed of 8000r/min for 10min, adding 5.3g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 505g of supported catalyst powder. 200g of deionized water, 300g of silicon dioxide and 35g of polyethylene glycol 6000 are added into 505g of the obtained supported catalyst powder, the mixture is fully mixed in a bonder, and is pressed into a bar in a bar press machine, the diameter of the bar press is 2mm, and then the bar press is cut into a cylinder with the length of 3 mm. And (3) drying at 120 ℃ in vacuum to obtain the loaded MMC-6.
[ example 7 ]
40g of polyoxypropylene glycol having a hydroxyl value of about 280.0mgKOH/g and 0.5g of a supported catalyst MMC-1 were charged into a 1L pressure-resistant reactor, and the pressure was increased to 120 ℃ or higher by vacuum pumping, 360g of propylene oxide was slowly charged while maintaining the pressure in the reactor at 0.15MPa or less, and when the pressure in the reactor became negative and did not decrease any more, it was confirmed that the reaction was completed for a total reaction time of 40 minutes, 398.2g of a catalyst-containing polyether diol was discharged by cooling. The hydroxyl value was 27.6mgKOH/g, the degree of unsaturation was 0.008mmol/g, and the molecular weight distribution was 1.06.
[ example 8 ]
The catalyst MMC-1 in the polyether discharged from example 7 was filtered, and again charged into the reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added to repeat example 7 to obtain 398g of polyether glycol having a hydroxyl value of 28.0mgKOH/g, an unsaturation value of 0.009mmol/g and a molecular weight distribution of 1.06.
[ example 9 ]
The catalyst MMC-1 in the polyether discharged from example 8 was filtered, and again charged into the reaction vessel, and similarly 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added to repeat example 8 to obtain 397g of polyether glycol having a hydroxyl value of 28.1mgKOH/g, an unsaturation value 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 having a hydroxyl value of 27.4mgKOH/g, an unsaturation value of 0.008mmol/g and a molecular weight distribution of 1.05 was obtained.
[ example 11 ]
The catalyst MMC-2 in the polyether discharged in example 10 was filtered out, added into the reaction kettle again, and 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added in the same manner, 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 having a hydroxyl value of 27.5mgKOH/g, an unsaturation value of 0.009mmol/g and a molecular weight distribution of 1.06 was obtained.
[ example 13 ]
The catalyst MMC-3 in the polyether discharged from example 12 was filtered, added again to the reaction vessel, and similarly, 40g of polyoxypropylene propylene glycol having a hydroxyl value of about 280.0mgKOH/g was added to repeat example 12 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 value of 0.009mmol/g and a molecular weight distribution of 1.06.
[ example 14 ]
50g of polyoxypropylene triol having a hydroxyl value of about 336.0mgKOH/g and 0.5g of catalyst MMC-1 were charged into a 1L pressure-resistant reactor, the temperature was raised to 120 ℃ by vacuum pumping, 250g of propylene oxide was slowly charged while maintaining the pressure in the reactor at not more than 0.15MPa, and when the pressure in the reactor became negative and did not decrease any more, it was confirmed that the reaction was completed for a total reaction time of 30 minutes, and cooled to obtain 298.0g of polyether triol. The hydroxyl value was 55.5mgKOH/g, the degree of unsaturation was 0.008mmol/g, and the molecular weight distribution was 1.09.
[ example 15 ]
The catalyst MMC-1 in polyether in example 14 was removed, filtered, charged into the reaction vessel again, and 50g of polyoxypropylene glycerol having a hydroxyl value of about 336.0mgKOH/g was similarly added to repeat example 14 to obtain 297g of polyether diol having a hydroxyl value of 56.0mgKOH/g, an unsaturation value of 0.009mmol/g and a molecular weight distribution of 1.09.
[ example 16 ]
The catalyst MMC-1 in the polyether discharged from example 15 was filtered off, and again charged into the reaction vessel, and similarly 50g of polyoxypropylene glycerol having a hydroxyl value of about 336.0mgKOH/g was added to repeat example 15 to obtain 297g of polyether triol having a hydroxyl value of 56.2mgKOH/g, an unsaturation value of 0.009mmol/g and a molecular weight distribution of 1.09.
Comparative example 1
5.6g K3[Co(CN)6]And 2.52g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of aqueous solution, then adding a mixed solution of 100mL of tert-butyl alcohol and 100mL of deionized water, then adding 26g of ethyl orthosilicate, stirring for 25min, then adding a mixed solution of 14.5g of dimethyl phthalate and 200mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. Finally, the obtained solid is added into the mixed solution of 150mL of tert-butyl alcohol and 50mL of deionized water, stirred for 10min at the speed of 8000r/min, and then added with 10.6g of dimethyl phthalateAfter stirring for 10min, the mixture was centrifuged. And adding 220mL of tert-butyl alcohol into the obtained solid, stirring for 10min at the speed of 8000r/min, adding 6.8g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 30g of white solid Cat-1.
40g of polyoxypropylene glycol having a hydroxyl value of about 280.0mgKOH/g and 0.5g of Cat-1 were charged into a 1L pressure-resistant reactor, and the pressure was increased to 120 ℃ or higher by vacuum pumping, 360g of propylene oxide was slowly charged while maintaining the pressure in the reactor at 0.15MPa or less, and when the pressure in the reactor became negative and did not decrease any more, it was confirmed that the reaction was completed for a total reaction time of 40 minutes, 399.0g of catalyst-containing polyether glycol was discharged by cooling. The hydroxyl value was 27.6mgKOH/g, the degree of unsaturation was 0.009mmol/g, and the molecular weight distribution was 1.07.
Filtering Cat-1 in the above-mentioned product, adding it into reaction still again, adding 40g of polyoxypropylene glycol whose hydroxyl value is about 280.0mgKOH/g, repeating the above-mentioned polymerization, after adding 20g of propylene oxide, stirring for 2 hr, the pressure does not drop, and it is proved that Cat-1 has no activity when it is reused.
Comparative example 2
5.6g K3[Co(CN)6]And 2.52g K2[CoFe(CN)6]Adding the mixture into 150mL of deionized water to dissolve the mixture, and adding 38.5 wt% of ZnCl into the mixture at a rotating speed of 8000r/min265g of the aqueous solution, then adding a mixed solution of 100mL of tert-butyl alcohol and 100mL of deionized water, then adding 26g of ethyl titanate, stirring for 25min, then adding a mixed solution of 14.5g of dimethyl phthalate and 200mL of deionized water, continuing stirring for 10min, and then carrying out vacuum filtration by using a sand core funnel. And finally, adding the obtained solid into a mixed solution of 150mL of tert-butyl alcohol and 50mL of deionized water, stirring at the speed of 8000r/min for 10min, adding 10.6g of dimethyl phthalate, stirring for 10min, and performing centrifugal separation. And adding 220mL of tert-butyl alcohol into the obtained solid, stirring for 10min at the speed of 8000r/min, adding 6.8g of dimethyl phthalate, stirring for 10min, performing centrifugal separation, and drying to obtain 33g of white solid Cat-2.
40g of polyoxypropylene glycol having a hydroxyl value of about 280.0mgKOH/g and 0.5g of Cat-2 were charged into a 1L pressure-resistant reactor, and the pressure was increased to 120 ℃ or higher by vacuum pumping, 360g of propylene oxide was slowly charged while maintaining the pressure in the reactor at 0.15MPa or less, and when the pressure in the reactor became negative and did not decrease any more, it was confirmed that the reaction was completed for a total reaction time of 40 minutes, and 397.0g of catalyst-carrying polyether diol was discharged by cooling. The hydroxyl value was 27.3mgKOH/g, the degree of unsaturation was 0.008mmol/g, and the molecular weight distribution was 1.08.
Filtering Cat-1 in the above-mentioned product, adding it into reaction still again, adding 40g of polyoxypropylene glycol whose hydroxyl value is about 280.0mgKOH/g, repeating the above-mentioned polymerization, after adding 20g of propylene oxide, stirring for 2 hr, the pressure does not drop, and it is proved that Cat-2 has no activity when it is reused.
As can be seen from comparison of comparative examples 1-2 with the examples, the catalyst cannot be reused due to the use of silica and titania as carriers, and probably because silica and titania have no proper pore channels, the adsorption force on the metal cyanide complex catalyst is weak; the molecular sieve has unique pore channels and adsorption performance, and can be adsorbed into the pore channels of the molecular sieve or enter the framework of the molecular sieve after being contacted with some metal ions, so that the catalyst with a specific catalytic effect (unexpected) is obtained.
Therefore, the supported metal cyanide complex catalyst prepared by the molecular sieve is unexpectedly found to be capable of being filtered and reused, and the defects that the existing metal cyanide complex has high cost, is difficult to remove and cannot be reused are overcome. And the environmental problem that the content of transition metal exceeds the standard due to the deposition of a metal cyanide complex catalyst in a polyether production device can be solved.