CN102580766A - Regeneration method of recycled Raney-Ni catalyst for EHA (2-ethylhexyl 4-(dimethylamino)benzoate) - Google Patents
Regeneration method of recycled Raney-Ni catalyst for EHA (2-ethylhexyl 4-(dimethylamino)benzoate) Download PDFInfo
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- CN102580766A CN102580766A CN2012100099215A CN201210009921A CN102580766A CN 102580766 A CN102580766 A CN 102580766A CN 2012100099215 A CN2012100099215 A CN 2012100099215A CN 201210009921 A CN201210009921 A CN 201210009921A CN 102580766 A CN102580766 A CN 102580766A
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Abstract
The invention relates to a regeneration method of a recycled Raney-Ni catalyst for EHA (2-ethylhexyl 4-(dimethylamino)benzoate). The method comprises the following steps of (1) carrying out alcohol-washing on inactivated Raney-Ni catalyst by 90-99% methyl alcohol; (2) carrying out water-washing by pure water; (3) carrying out alkali-etching by using sodium hydroxide solution; and (4) carrying out pure-water-washing by using a pouring method till the pH value of washing solution is 7-8. The method disclosed by the invention can be used for recovering the activity of the inactivated Raney-Ni catalyst to be 70-80% of that of a fresh Raney-Ni catalyst, and the regenerated Raney-Ni catalyst can be used for catalytic hydrogenation of EHA products independently or together with the fresh Raney-Ni catalyst, so that the consumption amount of the Raney-Ni catalyst for the EHA products per unit can be greatly reduced, and good economic benefits are obtained.
Description
Technical field
The present invention relates to a kind of EHA with the renovation process that reclaims the Raney-Ni catalyst.
Background technology
Raney-Ni (Raney's nickel) is a kind of metal Ni catalyst that spongy pore structure is arranged, and invention has developed into one type of broad-spectrum catalyst so far from nineteen twenty-five.What play active function in the Raney-Ni catalyst mainly is because there is the Ni activated centre in the blemish position, is the LINEAR N i-H surface species of weak absorption with the hydrogen molecule activation, makes it participate in hydrogenation reaction.
The Raney-Ni catalyst that uses in EHA (the different monooctyl ester of p-(dimethylamino)-benzoic acid) the hydrogenation production process finishes the back because the bigger oil product EHA of viscosity wraps catalyst granules at a batch reaction; Stop up the duct of skeleton nickel; Make the Raney-Ni activity of such catalysts to descend rapidly; The catalytic hydrogenation that can't recur if changing fresh catalyst again then can make ton consumption of product spent catalyst obviously raise, causes production cost to increase; Influence economic benefit, be unfavorable for resource recycling.
The general processing mode of inactivation Raney-Ni catalyst mainly contains following two kinds on the market now: 1. through inactivation Raney-Ni catalyst being washed, dries and reducing to handle and extract carbonyl nickel; 2. be raw material with inactivation Raney-Ni catalyst, the preparation nickel oxide, thus reach the purpose that reclaims nickel in the catalyst.And do not see in open source literature with the renovation process of inactivation Raney-Ni catalyst and mention to EHA.
Summary of the invention
The object of the present invention is to provide a kind of EHA with the renovation process that reclaims the Raney-Ni catalyst, this method is simple effectively, cost is low, can repeatedly recycle inactivation Raney-Ni catalyst.
For realizing above-mentioned purpose, the technical scheme that the present invention adopted is:
A kind of EHA comprises the steps: with the renovation process that reclaims the Raney-Ni catalyst
(1) using concentration is that 90 ~ 99% methyl alcohol carries out alcohol to inactivation Raney-Ni catalyst and washes;
(2) wash with pure water;
(3) carry out the alkali etch with sodium hydroxide solution;
(4) with the washing of decantation pure water, be 7 ~ 8 until the pH of cleaning solution value.
Further setting as such scheme; Alcohol in the said step (1) is washed and is specifically comprised inactivation Raney-Ni catalyst and 90 ~ 99% methyl alcohol are dropped in the containers by weight 1:3 ~ 6; Under stirring, be warming up to 40 ~ 60 ℃; Then under keeping warm mode, stirred 0.5 hour, under keeping warm mode, left standstill 0.5 hour then, at last upper strata methyl alcohol is separated.
Said alcohol is washed and will be carried out repeatedly 2 ~ 3 times.
Washing in the said step (2) comprises that specifically inactivation Raney-Ni catalyst and the pure water after alcohol washed drops in the containers by weight 1:3 ~ 6; Under stirring, be warming up to 70 ~ 95 ℃; Then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper aqueous layer is separated.
Said washing will be carried out 2 times repeatedly.
Alkali etch in the said step (3) specifically comprises according to the content of aluminium and the granularity of Raney-Ni catalyst in the inactivation Raney-Ni catalyst of washing back; Inactivation Raney-Ni catalyst is put into concentration by weight 1:2.5 ~ 5 be in 5 ~ 15% the sodium hydroxide solution; Under stirring, be warming up to 80 ~ 90 ℃; Then under keeping warm mode, stirred 1 hour, under keeping warm mode, left standstill 0.5 hour then.
The temperature of said sodium hydroxide solution before inactivation Raney-Ni catalyst input is controlled at below 50 ℃.
The temperature of said sodium hydroxide solution before inactivation Raney-Ni catalyst input is 30 ~ 40 ℃.
The invention has the beneficial effects as follows: through above-mentioned renovation process; Can make inactivation Raney-Ni activity of such catalysts return to 70 ~ 80% of fresh Raney-Ni catalyst activity; Raney-Ni catalyst after the regeneration can be separately or is mixed for the catalytic hydrogenation of EHA product with fresh catalyst; Significantly reduce the consumption of the Raney-Ni catalyst of the EHA of unit product, obtained favorable economic benefit.
The specific embodiment
The agitated reactor that with the volume is 1L below is a container, in conjunction with instance the present invention is described further.
Embodiment 1
A kind of EHA of the present invention carries out according to following steps with the renovation process that reclaims the Raney-Ni catalyst successively:
(1) using concentration is that 99% methyl alcohol carries out alcohol to inactivation Raney-Ni catalyst and washes; Specifically comprise: with inactivation Raney-Ni catalyst 110g; Drop among the methyl alcohol 500ml, under stirring, be warming up to 40 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper strata methyl alcohol is separated.Alcohol is washed 2 times repeatedly.
(2) wash with pure water; Specifically comprise adding pure water 400ml in the inactivation Raney-Ni catalyst after alcohol is washed, under stirring, be warming up to 70 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper aqueous layer is separated.Repeated water washing 2 times.
(3) carry out the alkali etch with sodium hydroxide solution, comprise that specifically sampling detects its aluminum content to the Raney-Ni catalyst after the washing, it is 3.20% that the result records aluminium content, size distribution 300 ~ 400 orders.Situation according to aluminium content and granularity; It is in 5% the sodium hydroxide solution that Raney-Ni catalyst after the washing is put into 350ml concentration; And the temperature of control sodium hydroxide solution when feeding intake is at 30 ℃, feed intake finish after, under stirring, be warming up to 80 ℃; Then under keeping warm mode, stirred 1 hour, under keeping warm mode, left standstill 0.5 hour then.
(4) with the washing of decantation pure water, be 7 until the pH of cleaning solution value, water seal is subsequent use.
Embodiment 2
A kind of EHA of the present invention carries out according to following steps with the renovation process that reclaims the Raney-Ni catalyst successively:
(1) using concentration is that 90% methyl alcohol carries out alcohol to inactivation Raney-Ni catalyst and washes; Specifically comprise: with inactivation Raney-Ni catalyst 110g; Drop among the methyl alcohol 500ml, under stirring, be warming up to 60 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper strata methyl alcohol is separated.Alcohol is washed 2 times repeatedly.
(2) wash with pure water; Specifically comprise adding pure water 400ml in the inactivation Raney-Ni catalyst after alcohol is washed, under stirring, be warming up to 95 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper aqueous layer is separated.Repeated water washing 2 times.
(3) carry out the alkali etch with sodium hydroxide solution, comprise that specifically sampling detects its aluminum content to the Raney-Ni catalyst after the washing, it is 5.35% that the result records aluminium content, size distribution 300 ~ 400 orders.Situation according to aluminium content and granularity; It is in 10% the sodium hydroxide solution that Raney-Ni catalyst after the washing is put into 350ml concentration; And the temperature of control sodium hydroxide solution when feeding intake is at 40 ℃, feed intake finish after, under stirring, be warming up to 90 ℃; Then under keeping warm mode, stirred 1 hour, under keeping warm mode, left standstill 0.5 hour then.
(4) with the washing of decantation pure water, be 8 until the pH of cleaning solution value, water seal is subsequent use.
Embodiment 3
A kind of EHA of the present invention carries out according to following steps with the renovation process that reclaims the Raney-Ni catalyst successively:
(1) using concentration is that 95% methyl alcohol carries out alcohol to inactivation Raney-Ni catalyst and washes; Specifically comprise: with inactivation Raney-Ni catalyst 110g; Drop among the methyl alcohol 500ml, under stirring, be warming up to 50 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper strata methyl alcohol is separated.Alcohol is washed 2 times repeatedly.
(2) wash with pure water; Specifically comprise adding pure water 400ml in the inactivation Raney-Ni catalyst after alcohol is washed, under stirring, be warming up to 80 ℃, then under keeping warm mode, stirred 0.5 hour; Under keeping warm mode, left standstill 0.5 hour then, at last upper aqueous layer is separated.Repeated water washing 2 times.
(3) carry out the alkali etch with sodium hydroxide solution, comprise that specifically sampling detects its aluminum content to the Raney-Ni catalyst after the washing, it is 9.70% that the result records aluminium content, size distribution 300 ~ 400 orders.Situation according to aluminium content and granularity; It is in 15% the sodium hydroxide solution that Raney-Ni catalyst after the washing is put into 350ml concentration; And the temperature of control sodium hydroxide solution when feeding intake is at 35 ℃, feed intake finish after, under stirring, be warming up to 85 ℃; Then under keeping warm mode, stirred 1 hour, under keeping warm mode, left standstill 0.5 hour then.
(4) with the washing of decantation pure water, be 7.6 until the pH of cleaning solution value, water seal is subsequent use.
Adopt the prepared regeneration of above three embodiment Raney-Ni catalyst to carry out the hydrogenation hydrogenation: regeneration Raney-Ni catalyst is used for the reduction hydrogenation of EHA; In full accord when reaction condition and new Raney-Ni catalyst applications; The time that EHA is reacted to terminal point is 20 hours; Slightly increased in 17 hours than raw catelyst, effect is obvious.
Contrast as follows with new Raney-Ni catalyst each item index behind the inactivation Raney-Ni catalyst regeneration:
The foregoing description only is used to the inventive concept of the present invention of explaining, but not to the qualification of rights protection of the present invention, allly utilizes this design that the present invention is carried out the change of unsubstantiality, all should fall into protection scope of the present invention.
Claims (8)
1. an EHA is characterized in that comprising the steps: with the renovation process that reclaims the Raney-Ni catalyst
(1) using concentration is that 90 ~ 99% methyl alcohol carries out alcohol to inactivation Raney-Ni catalyst and washes;
(2) wash with pure water;
(3) carry out the alkali etch with sodium hydroxide solution;
(4) with the washing of decantation pure water, be 7 ~ 8 until the pH of cleaning solution value.
2. a kind of EHA as claimed in claim 1 is with the renovation process that reclaims the Raney-Ni catalyst; It is characterized in that: the alcohol in the said step (1) is washed and is specifically comprised inactivation Raney-Ni catalyst and 90 ~ 99% methyl alcohol are dropped in the containers by weight 1:3 ~ 6; Under stirring, be warming up to 40 ~ 60 ℃; Then under keeping warm mode, stirred 0.5 hour, under keeping warm mode, left standstill 0.5 hour then, at last upper strata methyl alcohol is separated.
3. a kind of EHA as claimed in claim 2 is with the renovation process that reclaims the Raney-Ni catalyst, and it is characterized in that: said alcohol is washed and will be carried out repeatedly 2 ~ 3 times.
4. a kind of EHA as claimed in claim 1 is with the renovation process that reclaims the Raney-Ni catalyst; It is characterized in that: the washing in the said step (2) comprises that specifically inactivation Raney-Ni catalyst and the pure water after alcohol washed drops in the containers by weight 1:3 ~ 6; Under stirring, be warming up to 70 ~ 95 ℃; Then under keeping warm mode, stirred 0.5 hour, under keeping warm mode, left standstill 0.5 hour then, at last upper aqueous layer is separated.
5. a kind of EHA as claimed in claim 4 is with the renovation process that reclaims the Raney-Ni catalyst, and it is characterized in that: said washing will be carried out 2 times repeatedly.
6. a kind of EHA as claimed in claim 1 is with the renovation process that reclaims the Raney-Ni catalyst; It is characterized in that: the alkali etch in the said step (3) specifically comprises according to the content of aluminium and the granularity of Raney-Ni catalyst in the inactivation Raney-Ni catalyst of washing back; Inactivation Raney-Ni catalyst is put into concentration by weight 1:2.5 ~ 5 be in 5 ~ 15% the sodium hydroxide solution; Under stirring, be warming up to 80 ~ 90 ℃; Then under keeping warm mode, stirred 1 hour, under keeping warm mode, left standstill 0.5 hour then.
7. a kind of EHA as claimed in claim 6 is characterized in that with the renovation process that reclaims the Raney-Ni catalyst: the temperature of said sodium hydroxide solution before inactivation Raney-Ni catalyst input is controlled at below 50 ℃.
8. a kind of EHA as claimed in claim 7 is characterized in that with the renovation process that reclaims the Raney-Ni catalyst: the temperature of said sodium hydroxide solution before inactivation Raney-Ni catalyst input is 30 ~ 40 ℃.
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| CN 201210009921 CN102580766B (en) | 2012-01-13 | 2012-01-13 | Regeneration method of recycled Raney-Ni catalyst for EHA (2-ethylhexyl 4-(dimethylamino)benzoate) |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435208A (en) * | 2018-05-09 | 2018-08-24 | 安庆市鑫富化工有限责任公司 | A kind of regeneration technology of catalyst Raney's nickel and its application |
| CN110813385A (en) * | 2018-08-09 | 2020-02-21 | 安徽泰格维生素科技有限公司 | Regeneration method of Raney nickel catalyst |
| CN112495397A (en) * | 2019-10-22 | 2021-03-16 | 江苏维尤纳特精细化工有限公司 | Activation regeneration method of Raney nickel catalyst used for producing m-xylylenediamine |
| CN112517024A (en) * | 2020-12-03 | 2021-03-19 | 安道麦安邦(江苏)有限公司 | Method for regenerating inactivated pirimiphos-methyl Raney nickel catalyst |
| CN113649084A (en) * | 2021-09-08 | 2021-11-16 | 天津理工大学 | Method for restoring activity of safe porous nickel catalyst |
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| GB1202711A (en) * | 1967-01-20 | 1970-08-19 | Ici Ltd | Catalyst regeneration process |
| CN1410162A (en) * | 2001-09-26 | 2003-04-16 | 北京理工大学 | Recovering method of hydrogenation catalyst nickel in nafronyl oxalate |
| CN101492380A (en) * | 2008-12-17 | 2009-07-29 | 鲁南制药集团股份有限公司 | Process for producing miglitol key intermediate |
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2012
- 2012-01-13 CN CN 201210009921 patent/CN102580766B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB1202711A (en) * | 1967-01-20 | 1970-08-19 | Ici Ltd | Catalyst regeneration process |
| CN1410162A (en) * | 2001-09-26 | 2003-04-16 | 北京理工大学 | Recovering method of hydrogenation catalyst nickel in nafronyl oxalate |
| CN101492380A (en) * | 2008-12-17 | 2009-07-29 | 鲁南制药集团股份有限公司 | Process for producing miglitol key intermediate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108435208A (en) * | 2018-05-09 | 2018-08-24 | 安庆市鑫富化工有限责任公司 | A kind of regeneration technology of catalyst Raney's nickel and its application |
| CN110813385A (en) * | 2018-08-09 | 2020-02-21 | 安徽泰格维生素科技有限公司 | Regeneration method of Raney nickel catalyst |
| CN112495397A (en) * | 2019-10-22 | 2021-03-16 | 江苏维尤纳特精细化工有限公司 | Activation regeneration method of Raney nickel catalyst used for producing m-xylylenediamine |
| CN112517024A (en) * | 2020-12-03 | 2021-03-19 | 安道麦安邦(江苏)有限公司 | Method for regenerating inactivated pirimiphos-methyl Raney nickel catalyst |
| CN113649084A (en) * | 2021-09-08 | 2021-11-16 | 天津理工大学 | Method for restoring activity of safe porous nickel catalyst |
| CN113649084B (en) * | 2021-09-08 | 2024-02-23 | 天津理工大学 | Method for recovering activity of safe porous nickel catalyst |
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