CN105061748A - Attapulgite loaded hydrotalcite-like compound catalyst for polyether polyol synthesis and preparation method of hydrotalcite-like catalyst - Google Patents
Attapulgite loaded hydrotalcite-like compound catalyst for polyether polyol synthesis and preparation method of hydrotalcite-like catalyst Download PDFInfo
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- CN105061748A CN105061748A CN201510421091.0A CN201510421091A CN105061748A CN 105061748 A CN105061748 A CN 105061748A CN 201510421091 A CN201510421091 A CN 201510421091A CN 105061748 A CN105061748 A CN 105061748A
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Abstract
The invention relates to an attapulgite loaded hydrotalcite-like compound catalyst for polyether polyol synthesis and a preparation method of the hydrotalcite-like compound catalyst. Attapulgite is taken as the raw material and loaded with a hydrotalcite-like compound with a solution infiltration method, and the attapulgite loaded hydrotalcite-like compound catalyst is prepared, wherein the mass percentage of the hydrotalcite-like compound in the catalyst is 20%-25%. The preparation process of the catalyst is simple, the production cost is lower, the catalyst shows good reactivity and catalytic efficiency when used for synthesizing polyether polyol, and the obtained polyether polyol product has narrow molecular weight distribution range, low degree of unsaturation and light color.
Description
Technical field
The present invention relates to a kind of polyether glycol synthesis attapulgite loaded houghite Catalysts and its preparation method, belong to the field of catalyzing and synthesizing.
Background technology
Polyether glycol is a family macromolecule compound prepared by initiator and epoxy alkane ring opening polymerization by small molecule polyol or other active hydrogen compounds such as amine, hydramine, it is very important industrial chemicals, be widely used in the industry such as papermaking, weaving, printing and dyeing, synthetic leather, coating, tackiness agent, elastomerics, porous plastics, sealing agent and oil development, be the main raw material producing polyurethane product, there is very important effect in the industrial production.But the production of current domestic polyether product still adopts traditional base catalysis technique, and in product, average functionality is low, and degree of unsaturation is high, has had a strong impact on the performance of product.
Since industrialization, polyether glycol is produced used catalyst and is mainly contained anionic catalyzer, cationic catalyst and metal complexed catalyzer.Conventional anionic catalyzer is basic metal, is also catalyzer the most frequently used in current industrial production, but to have average functionality low for the polyether product that basic metal catalyzes and synthesizes, the complicated shortcoming such as loaded down with trivial details of the wide and aftertreatment technology of range of molecular weight distributions.Although utilize cationic catalyst can obtain narrow ditribution product, it can only generate the low product of relative molecular mass, and not only by product is many, and equipment corrosion is serious, but also can produce poisonous diox, seriously limits its application in the industrial production.As the metal complexed catalyzer of most industrial prospect, represent the trend of world today's polyethers synthesis development.Domestic and international researcher has done a large amount of research work for bimetal solvay-type catalyzer, as patent US5545601, WO97/40086, EP-A761708, WO00/47650 reports, and adopt the trimethyl carbinol as organic complex part, the catalyzer obtained has higher degree of crystallinity, shorten induction time when producing polyether glycol, improve catalyst activity.DMC catalysts prepared by patent CN1478803A proposition organic ligand, fluorine-containing part and metal-salt has good catalytic activity, and the phenomenon can effectively avoiding polyethers relative molecular mass to trail.Chinese patent CN1740208A discloses a kind of calcium sulfate, barium sulfate as the DMC catalysts of carrier, and the polyethers relative molecular weight of synthesis is narrow and without the need to removing residual catalyzer from polyethers.US Patent No. 8933192, US006291388, it is narrow that DMC catalysts disclosed in US20140228537 all has product molecular weight distribution prepared by good catalytic activity, and due to catalyst loading few, do not need to carry out aftertreatment and just can be directly used in the synthesis of urethane and the processing characteristics of goods can not be affected.
Nonetheless, still also there is many deficiencies in metal complexed catalyzer, such as small molecular alcohol easily makes partial metal complex catalyst deactivation, need oligopolymer as initiator when synthesizing, preparation technology's very complicated, cost is high, and metal complex catalyst directly can not complete the problems such as the end-blocking of oxyethane on propylene oxide polyether polyvalent alcohol.Therefore, improve existing polyethers synthetic catalyst or develop new catalyzer and it is successfully applied in suitability for industrialized production and play important pushing effect by the development of polyether glycol, there is good industrial value.
Summary of the invention
The object of the invention is to: a kind of polyether glycol synthesis attapulgite loaded houghite Catalysts and its preparation method is provided, prepared catalyzer is used for the synthesis of catalysis polyether glycol, there is good reactive behavior and catalytic efficiency, the Contents In Polyether Polyol range of molecular weight distributions obtained is narrow, and degree of unsaturation is low, lighter color.
For achieving the above object, the technical solution that the present invention adopts is:
Attapulgite loaded houghite catalyzer is that raw material is obtained by solution dipping method load houghite with attapulgite, and described houghite is magnesia-alumina hydrotalcite (Mg-Al-HTlc), and the mass percent that houghite accounts for catalyzer is 20-25%.
Wherein, Mg in described houghite
2+: Al
3+(mol ratio)=2 ~ 5:1.
Wherein, the preparation method of polyether glycol synthesis attapulgite loaded houghite catalyzer comprises the following steps:
(1) preparation of houghite: the preparation of houghite: by NaOH solution, Na
2cO
3solution, Mg (NO
3)
26H
2o solution and Al (NO
3)
39H
2the each 10mL of O solution instills in the 100mL deionized water of constant temperature 60 DEG C in the mode also flowed, and keeps pH value of solution constant; After dripping off, constant temperature stirs 30-60min, slurries is put into 100 DEG C of baking oven crystallization 8-12h, and crystallization process ensures that moisture is sufficient; Crystallization rear slurry through suction filtration, wash to filtrate in neutral, 80 DEG C of baking oven drying for standby put into by filter cake;
(2) load of houghite and attapulgite: the biased sample of the houghite prepared in 15g step (1) and attapulgite is added in 200mL deionized water, ultrasonic mixing 30-60min, wherein attapulgite and houghite mass ratio are 4 ~ 5:1; Then constant temperature 60 DEG C stirs 2h, has stirred rear standing 1h, and suction filtration is extremely neutral, 80 DEG C of oven dry; Then retort furnace is put into, 400-600 DEG C of roasting 5-10h, obtained attapulgite loaded houghite catalyzer.
Wherein, in step 1), the molar relationship of solution in step 1):
.
Wherein, in step 1), constant pH is 8-10.
Wherein, step 2), attapulgite is high-purity powder clay JC-C303, purity >=99.5% of Jiangsu Jiuchuan Clunch Technology Development Co., Ltd..
The invention has the beneficial effects as follows:
1, the present invention adopts attapulgite as support of the catalyst, make houghite evengranular be distributed in its surface, the specific surface area that attapulgite is large avoids the generation of houghite particle agglomeration, avoids reunion benefit and causes specific surface area to diminish, the problem that catalytic performance declines.
2, houghite is after high-temperature calcination, becomes complex metal oxides, has nano level micropore, is dispersed with a large amount of basic center that can make fatty alcohol and epoxy alkane generation ring-opening reaction in these micropores, for reaction provides enough active centre.
3, the attapulgite loaded catalyzer of preparation has very strong adsorptive power and Studies On The Shape-selective Catalysis, and it can make the rate of growth of the molecular chain being in the chainpropagation stage can not be soon unconfined, is conducive to the product forming narrow molecular weight distribution.
Embodiment
Further describe technical solution of the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as it is restriction to technical scheme.Reagent, equipment that the present invention adopts are conventional commercial reagent, the equipment of the art.
Embodiment 1: prepare attapulgite loaded houghite catalyzer according to following steps
(1) preparation of houghite: by NaOH(6mol/L) solution, Na
2cO
3(0.5mol/L) solution, Mg (NO
3)
26H
2o(2mol/L) solution, Al (NO
3)
39H
2o(1mol/L) each 10mL of solution instills in the 100mL deionized water of constant temperature 60 DEG C in the mode also flowed, and keeping pH value of solution constant is 8; After dripping off, constant temperature stirs 30min, slurries is put into 100 DEG C of baking oven crystallization 8h, and crystallization process ensures that moisture is sufficient; Crystallization rear slurry through suction filtration, wash to filtrate in neutral, 80 DEG C of baking oven drying for standby put into by filter cake;
(2) load of houghite and attapulgite: houghite 3g obtained in attapulgite 12g, step (1) is added in 200mL deionization, ultrasonic mixing 30min; Then constant temperature 60 DEG C stirs 2h, has stirred rear standing 1h, and suction filtration is extremely neutral, 80 DEG C of oven dry; Then retort furnace is put into, 400 DEG C of roasting 5h, obtained attapulgite loaded houghite catalyzer.
Embodiment 2: prepare attapulgite loaded houghite catalyzer according to following steps
(1) preparation of houghite: by NaOH(4.8mol/L) solution, Na
2cO
3(0.2mol/L) solution, Mg (NO
3)
26H
2o(2mol/L) solution, Al (NO
3)
39H
2o(0.4mol/L) each 10mL of solution instills in the 100mL deionized water of constant temperature 60 DEG C in the mode also flowed, and keeping pH value of solution constant is 10; After dripping off, constant temperature stirs 60min, slurries is put into 100 DEG C of baking oven crystallization 12h, and crystallization process ensures that moisture is sufficient; Crystallization rear slurry through suction filtration, wash to filtrate in neutral, 80 DEG C of baking oven drying for standby put into by filter cake;
(2) load of houghite and attapulgite: houghite 2.5g obtained in attapulgite 12.5g, step (1) is added in 200mL deionization, ultrasonic mixing 60min; Then constant temperature 60 DEG C stirs 2h, has stirred rear standing 1h, and suction filtration is extremely neutral, 80 DEG C of oven dry; Then retort furnace is put into, 400 DEG C of roasting 10h, obtained attapulgite loaded houghite catalyzer.
Embodiment 3: prepare attapulgite loaded houghite catalyzer according to following steps
(1) preparation of houghite: by NaOH(5mol/L) solution, Na
2cO
3(0.25mol/L) solution, Mg (NO
3)
26H
2o(2mol/L) solution, Al (NO
3)
39H
2o(0.5mol/L) each 10mL of solution instills in the 100mL deionized water of constant temperature 60 DEG C in the mode also flowed, and keeping pH value of solution constant is 9; After dripping off, constant temperature stirs 50min, slurries is put into 100 DEG C of baking oven crystallization 10h, and crystallization process ensures that moisture is sufficient; Crystallization rear slurry through suction filtration, wash to filtrate in neutral, 80 DEG C of baking oven drying for standby put into by filter cake;
(2) load of houghite and attapulgite: houghite 2.8g obtained in attapulgite 12.2g, step (1) is added in 200mL deionization, ultrasonic mixing 40min; Then constant temperature 60 DEG C stirs 2h, has stirred rear standing 1h, and suction filtration is extremely neutral, 80 DEG C of oven dry; Then retort furnace is put into, 500 DEG C of roasting 8h, obtained attapulgite loaded houghite catalyzer.
Embodiment 4: in the preparation of step (1) houghite, pH value is held constant at 10, churning time is 60min, and crystallization time is 12h, and in the load of the middle houghite of step (2) and attapulgite, maturing temperature is 600 DEG C, the other the same as in Example 1.
Embodiment 5: in the preparation of step (1) houghite, pH value keeps pH value of solution constant is 8; In the load of the middle houghite of step (2) and attapulgite, roasting time is 8h, and maturing temperature is 600 DEG C, the other the same as in Example 2.
Embodiment 6: in the load of the middle houghite of step (2) and attapulgite, roasting time is 5h, and maturing temperature is 600 DEG C, the other the same as in Example 3.
Application examples: the synthesis of the load houghite catalyst polyether glycol of attapulgite
C is added in the autoclave of 1L
12-C
14(100g) with arbitrary catalyzer (3g) in above-described embodiment 1-6, be warming up to 120 DEG C, decompression dehydration 30min, period, with nitrogen replacement several, is warming up to 160-170 DEG C, drops into a small amount of oxyethane induced reaction, control pressure is less than 0.4MPa, question response pressure obviously reduces, and when temperature sharply rises, shows that catalyzer activates; Pass into oxyethane gradually, treat that still internal pressure no longer reduces, continue insulation reaction 30min, the unreacted monomer of removed under reduced pressure, 60 DEG C of dischargings, filtrations obtain Contents In Polyether Polyol, reclaim catalyzer.
Result shows: with obtained catalyst C
12-C
14polyether glycol has been synthesized with reacting ethylene oxide, reaction is started as temperature > 150 DEG C, product ethylene oxide dispersion index is all more than 80%, catalyzer particularly prepared by embodiment 3, the product oxyethane dispersion index catalyzed and synthesized reaches 85%, far away higher than the product of KOH catalysis, illustrate that obtained catalyzer is the molecular weight narrow ditribution catalyzer of better performances.Product iodine number is at 0.05-0.1gI
2between/100g, illustrate that product degree of unsaturation is low, side reaction is less.And product easily filters, do not need to add sorbent material decolouring and just obtain the more shallow product of color and luster.
Claims (6)
1. polyether glycol synthesis attapulgite loaded houghite catalyzer, attapulgite loaded houghite catalyzer is that raw material is obtained by solution dipping method load houghite with attapulgite, it is characterized in that: described houghite is magnesia-alumina hydrotalcite (Mg-Al-HTlc), the mass percent that houghite accounts for catalyzer is 20-25%.
2. polyether glycol synthesis attapulgite loaded houghite catalyzer according to claim 1, is characterized in that: Mg in described houghite
2+: Al
3+(mol ratio)=2 ~ 5:1.
3. the polyether glycol synthesis preparation method of attapulgite loaded houghite catalyzer, is characterized in that this preparation method comprises the following steps:
(1) preparation of houghite: by NaOH solution, Na
2cO
3solution, Mg (NO
3)
26H
2o solution and Al (NO
3)
39H
2the each 10mL of O solution instills in the 100mL ionized water of constant temperature 60 DEG C in the mode also flowed, and keeps pH value of solution constant; After dripping off, constant temperature stirs 30-60min, slurries is put into 100 DEG C of baking oven crystallization 8-12h, and crystallization process ensures that moisture is sufficient; Crystallization rear slurry through suction filtration, wash to filtrate in neutral, 80 DEG C of baking oven drying for standby put into by filter cake;
(2) load of houghite and attapulgite: the biased sample of the houghite prepared in 15g step (1) and attapulgite is added in 200mL deionized water, ultrasonic mixing 30-60min, wherein attapulgite and houghite mass ratio are 4 ~ 5:1; Then constant temperature 60 DEG C stirs 2h, has stirred rear standing 1h, and suction filtration is extremely neutral, 80 DEG C of oven dry; Then retort furnace is put into, 400-600 DEG C of roasting 5-10h, obtained attapulgite loaded houghite catalyzer.
4. the preparation method of polyether glycol synthesis attapulgite loaded houghite catalyzer according to claim 3, is characterized in that: the molar relationship of solution in step 1):
.
5. the preparation method of polyether glycol synthesis attapulgite loaded houghite catalyzer according to claim 3, it is characterized in that: in step 1), constant pH is 8-10.
6. the preparation method of polyether glycol synthesis attapulgite loaded houghite catalyzer according to claim 3, it is characterized in that: step 2) in, described attapulgite is high-purity powder clay JC-C303, purity >=99.5% of Jiangsu Jiuchuan Clunch Technology Development Co., Ltd..
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358608A (en) * | 2020-10-29 | 2021-02-12 | 江苏利宏科技发展有限公司 | Preparation method of polyether polyol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN1493393A (en) * | 2003-08-25 | 2004-05-05 | 浙江大学 | Adsorber for removing antiseptic byproduct in city water and its preparation and use method |
-
2015
- 2015-07-17 CN CN201510421091.0A patent/CN105061748B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275442A (en) * | 1999-05-26 | 2000-12-06 | 中国科学院大连化学物理研究所 | Waterlike talc solid catalyst for production of triethyl glycol monoethers |
| CN1493393A (en) * | 2003-08-25 | 2004-05-05 | 浙江大学 | Adsorber for removing antiseptic byproduct in city water and its preparation and use method |
Non-Patent Citations (1)
| Title |
|---|
| 周述慧, 叶巧明: "矿物材料在催化领域中的应用", 《应用化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358608A (en) * | 2020-10-29 | 2021-02-12 | 江苏利宏科技发展有限公司 | Preparation method of polyether polyol |
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