CN101024195A - Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use - Google Patents
Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use Download PDFInfo
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- CN101024195A CN101024195A CN 200710008734 CN200710008734A CN101024195A CN 101024195 A CN101024195 A CN 101024195A CN 200710008734 CN200710008734 CN 200710008734 CN 200710008734 A CN200710008734 A CN 200710008734A CN 101024195 A CN101024195 A CN 101024195A
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Abstract
The invention relates to a method of prepared 1,4-butyne glycol complex oxide catalyst with the HZSM-5 carrier and its application. The features are that: used the deionized water to make Cu(NO3)2.3H2O,Bi(NO3)3.5H2O and HNO3 mix into solution by the weight rate of 40-80:30-60:3-8:1. the prepared solution with high solicon molecular sieve (HZSM-5)1-1.5:2 mixing, string, dipping, through drying, grinding, roasting to get HZSM-5 load catalyst. Put the catalyst and formalin solution into the reaction kettle, the oil temperature up to 80-95degree centigrade, put the acetylene gas into reaction kettle process the ketenes and alkyne reaction of formalin. The invention catalyst of HZSM-5 carrier have better thermal stability, high activity, good selectivity, simple preparation method, can use the high condense formalin solution to react, it is suitable for synthetic 1,4-butyne glycol, reduce the treatment energy loss in the industry.
Description
Technical field
The present invention relates to a kind of is the molecular sieve catalyst of carrier with HZSM-5, particularly relates to a kind of formaldehyde ethinylation that can be applicable to and synthesizes 1, the preparation method and the application thereof of 4-butynediols composite oxide catalysts.
Background technology
1,4-butynediols (BD) is through 1 of the catalytic hydrogenation preparation, and 4-butanediol (BDO) is a kind of important organic synthesis intermediate, is used to produce gamma-butyrolacton (GBL), oxolane (THF), poly-two phthalic acid butanediol esters (PBT) etc.Domestic THF is annual to be needed more than the import 5000t, does not also have producer, a product dependence on import and the poly-tetramethylenthanediol ether (PTMEG) of the main users of THF is domestic.China will increase substantially to the demand of BDO, become one of industrial chemicals very in short supply.There is abundant calcium carbide in China, therefore be raw material with the calcium carbide, produce 1,4-butynediols and 1, the 4-butanediol has advantageous condition and advantage, but China's formaldehyde ethinylation catalysts development is started late, though many catalyst achievements can reach foreign level on activity, but on cost can't with the competition of external catalyst, have complex manufacturing, problem such as product yield is low, and catalyst mainly from external import, costs an arm and a leg.
Summary of the invention
The object of the present invention is to provide that a kind of preparation technology is simple, to can be applicable to the formaldehyde ethinylation synthetic 1, the composite oxide catalysts of 4-butynediols.It is characterized in that: with deionized water with Cu (NO
3)
23H
2O, Bi (NO
3)
35H
2O and HNO
3Be mixed with mixed solution, above-mentioned solution poured into stirred dipping in the beaker that high-silica zeolite (HZSM-5) is housed, the solution behind the dipping carries out drying, grinding and roasting together with the solid in the solution, obtains the grey powder, promptly obtains the catalyst of HZSM-5 load.Catalyst and formalin are put into reactor, and reactor is placed constant temperature oil bath, feed N
2Gas is forced sky with the air in the reactor, the heating reduction catalyst, and temperature rises to 80～95 ℃, closes N
2, change the feeding acetylene gas and carry out the generation of acetylenic ketone and the ethynylation of formaldehyde.
The present invention realizes above-mentioned technical characterictic by following concrete steps:
(1) with deionized water, Cu (NO
3)
23H
2O, Bi (NO
3)
35H
2O and HNO
3Be 40～80: 30～60 by weight: 3～8: 1 is hybridly prepared into solution.
(2) take by weighing solid HZSM-5 (Si/Al=38) and put into beaker, above-mentioned solution is added by solid-to-liquid ratio 1～1.5: 2 stir dipping in the beaker, dip time is 5～8 hours.
(3) solution after directly will flooding together with the solid in the solution in 120 ℃ of dryings 12～16 hours.
(4) grind and roasting after the cooling, 480～630 ℃ of sintering temperatures, and in this temperature range, keep under a certain steady temperature roasting continuously 5～7 hours, obtain the grey powder, i.e. the catalyst of HZSM-5 loaded copper oxide, bismuth oxide.Wherein containing weight of copper is 25～30%, and bismuth-containing weight is 4～6%.Optimum calcination temperature is between 550～600 ℃.Roasting process of the present invention is: temperature rises to the required temperature of roasting with 50～70 ℃ speed per hour.
(5) stir and intermittence of condensing unit in the stirred autoclave being equipped with, the 50mL formalin of the catalyst and 15～37% (percentage by weight) of adding 2.0～6.0g, and reactor placed constant temperature oil bath.Earlier logical N
2Air in the reactor is forced sky, heating reduction catalyst then, temperature rises to 80～95 ℃, closes N
2, feeding acetylene gas and carry out the generation of acetylenic ketone and the ethynylation of formaldehyde, the reaction time is between 24～28 hours.Be reflected under the normal pressure and carry out.
Cupric oxide in the catalyst is through having reacted catalytic action with the acetylenic ketone complex compound PARA FORMALDEHYDE PRILLS(91,95) ethinylation of formaldehyde and acetylene reaction generation, and the Bi in the bismuth oxide has inhibition Cu
IBe reduced into Cu
OEffect, thereby suppress the generation of carbene.
Select for use 5g catalyst of the present invention to do the decay of activity test, carried out 4 tests altogether, each reaction finishes, treat to filter after the abundant sedimentation of catalyst, filter residue relays the bottle that flashes back and adds fresh raw material formalin (36.2%), reacts again next time, and the reaction time is 24 hours.After measured, the formaldehyde conversion ratio is respectively 94.5%, 90.5%, and 90.3% and 89.5%.
Of the present invention is that the catalyst of carrier has the following advantages with HZSM-5:
1. of the present invention is the catalyst of carrier with HZSM-5, active high, and selectivity is good, and is activity stabilized, and Preparation of Catalyst is simple, is applicable to that slurry bed technology is synthetic 1, the 4-butynediols.
2. of the present invention is that the catalyst of carrier has good heat endurance with HZSM-5, can operate under normal pressure, reduces the danger that acetylene is blasted.
3. of the present invention is the catalyst of carrier with HZSM-5, but the formalin of applying high density react, in industrial energy resource consumption when reducing post processing.
The specific embodiment
Example 1
With the 50mL deionized water with 40.6g Cu (NO
3)
23H
2O, 5.0g Bi (NO
3)
35H
2O and 1.0gHNO
3Be made into mixed solution, take by weighing 20gHZSM-5 (Si/Al=38) and put into beaker, get above-mentioned solution 37g and pour stirring dipping in the beaker into, dip time is 5 hours.Solution after directly will flooding 120 ℃ of dryings, grinding, 480 ℃ of following roastings 6 hours, obtains the grey powder together with the solid in the solution, i.e. the catalyst of HZSM-5 loaded copper oxide, bismuth oxide, and wherein containing weight of copper is 25%, bismuth-containing weight is 6%.。
Example 2
With the 75mL deionized water with 35.0g Cu (NO
3)
23H
2O, 7.0g Bi (NO
3)
35H
2O and 1.0gHNO
3Be made into mixed solution, take by weighing 15.0g HZSM-5 (Si/Al=38) and put into beaker, get above-mentioned solution 30.0g and pour stirring dipping in the beaker into, dip time is 8 hours.Solution after directly will flooding 120 ℃ of dryings, grinding, 600 ℃ of following roastings 5 hours, obtains the grey powder together with the solid in the solution, and promptly wherein to contain weight of copper be 23% to the catalyst of HZSM-5 loaded copper oxide, bismuth oxide, and bismuth-containing weight is 6.5%.
Example 3
With the 40mL deionized water with 55.0g Cu (NO
3)
23H
2O, 4.0g Bi (NO
3)
33H
2O and 1.0gHNO
3Be made into mixed solution, take by weighing 20g HZSM-5 (Si/Al=38) and put into beaker, get above-mentioned solution 33g and pour stirring dipping in the beaker into, dip time is 6.5 hours.Solution after directly will flooding 120 ℃ of dryings, grinding, 550 ℃ of following roastings 6 hours, obtains the grey powder together with the solid in the solution, and promptly wherein to contain weight of copper be 30% to the catalyst of HZSM-5 loaded copper oxide, bismuth oxide, and bismuth-containing weight is 5.0%.
The formalin 50mL that gets above-mentioned catalyst 5g and 36.2% concentration puts into the reactor that is connected to stirring and condensing unit, and places constant temperature oil bath.Earlier logical N
2Air in the reactor is forced sky, heating reduction catalyst then, temperature rises to 90 ℃, closes N
2Gas changes the feeding acetylene gas and carries out the generation of acetylenic ketone and the ethynylation of formaldehyde.Be reflected under the normal pressure and carry out.React after 24 hours, the formaldehyde conversion ratio is 93.0%, and the butynediols selectivity is more than 98.8%.
Example 4
With the 60mL deionized water with 58.0g Cu (NO
3)
23H
2O, 8.0g Bi (NO
3)
35H
2O and 1.0gHNO
3Be made into mixed solution, take by weighing 10.0g HZSM-5 (Si/Al=38) and put into beaker, get above-mentioned solution 20.0g and pour stirring dipping in the beaker into, dip time is 5.0 hours.Solution after directly will flooding 120 ℃ of dryings, grinding, 580 ℃ of following roastings 6 hours, obtains the grey powder together with the solid in the solution, and promptly wherein to contain weight of copper be 33% to the catalyst of HZSM-5 loaded copper oxide, bismuth oxide, and bismuth-containing weight is 6.7%.
The formalin 50mL that gets above-mentioned catalyst 5g and 36.2% concentration puts into the stirred reactor that is connected to stirring and condensing unit, and places constant temperature oil bath.Earlier logical N
2Air in the reactor is forced sky, heating reduction catalyst then, temperature rises to 86 ℃, closes N
2Gas changes the feeding acetylene gas and carries out the generation of acetylenic ketone and the ethynylation of formaldehyde.Be reflected under the normal pressure and carry out.React after 28 hours, the formaldehyde conversion ratio is 93.8%, and the butynediols selectivity is more than 98.8%.
Example 5
Identical with embodiment 3 described reaction units with reaction condition, change initial concentration of formaldehyde and react, initial concentration of formaldehyde is respectively 20%, 25%, 28%, 30% and 37% o'clock, the conversion ratio of formaldehyde is respectively 91.1%, 90.6%, 90.3%, 90.1% and 89.6%.
Example 6
Identical with embodiment 4 described reaction units with reaction condition, change reaction temperature, at 70 ℃, 80 ℃, react under 90 ℃, the conversion ratio of formaldehyde is respectively 51.5%, 81.8%, 90.9% and 90.9%, the selectivity of butynediols is respectively 75.5%, 90.8% and 98.3%.
Example 7: in embodiment 3 described reaction units, add the catalyst of different amounts, add catalyst 2g, 4g among the formalin 50mL of 36.2% concentration respectively, 5g, 6g, with example 3 the same terms under react, the conversion ratio of formaldehyde is respectively 75%, 83%, 90.3% and 93.9%, the butynediols selectivity is respectively 82.7%, 97.0%, 98.5% and 98.8%.
Claims (10)
1, a kind of is the preparation method of the molecular sieve composite oxide catalyst of carrier with HZSM-5, it is characterized in that with deionized water Cu (NO
3)
23H
2O, Bi (NO
3)
35H
2O and HNO
3Be mixed with mixed solution, above-mentioned solution poured into stirred dipping in the beaker that HZSM-5 is housed, the solution behind the dipping carries out drying, grinding and roasting together with the solid in the solution, obtains the grey powder, promptly obtains the catalyst of HZSM-5 load.
2, HZSM-5 according to claim 1 is the preparation method of the molecular sieve composite oxide catalyst of carrier, it is characterized in that deionized water, Cu (NO
3)
23H
2O, Bi (NO
3)
35H
2O and HNO
3Be 40～80: 30～60 by weight: 3～8: 1 is hybridly prepared into solution.
3, HZSM-5 according to claim 1 is the preparation method of the molecular sieve composite oxide catalyst of carrier, the use silica alumina ratio is 38 solid HZSM-5 when it is characterized in that flooding, mix the stirring dipping by solid-to-liquid ratio 1～1.5: 2, dip time is 5～8 hours.
4, HZSM-5 according to claim 1 is the preparation method of the molecular sieve composite oxide catalyst of carrier, and temperature is 120 ℃ when carrying out drying after it is characterized in that flooding, dry 12～16 hours.
5, HZSM-5 according to claim 1 is the preparation method of the molecular sieve composite oxide catalyst of carrier, it is characterized in that described sintering temperature is 480～630 ℃, roasting 5～7 hours, the roasting process temperature rises to the required temperature of roasting with 50～70 ℃ speed per hour.
6, HZSM-5 according to claim 5 is the preparation method of the molecular sieve composite oxide catalyst of carrier, it is characterized in that described optimum calcination temperature is between 550～600 ℃.
7, a kind of is that the molecular sieve composite oxide catalyst of carrier is applied to formaldehyde ethinylation synthetic 1 with HZSM-5, the method of the ethynylation of the generation of acetylenic ketone and formaldehyde in the 4-butynediols process, it is characterized in that catalyst and formalin are put into reactor, the heating reduction catalyst feeds acetylene gas and carries out 24～28 hours the generation of acetylenic ketone and the ethynylation of formaldehyde.
8, according to claim 7 is that the molecular sieve composite oxide catalyst of carrier is applied to formaldehyde ethinylation synthetic 1 with HZSM-5, the method of the ethynylation of the generation of acetylenic ketone and formaldehyde in the 4-butynediols process, when it is characterized in that heat temperature raising reactor is placed constant temperature oil bath, feed N simultaneously
2Air in the reactor is forced sky.
9, according to claim 7 is that the molecular sieve composite oxide catalyst of carrier is applied to formaldehyde ethinylation synthetic 1 with HZSM-5, the method of the ethynylation of the generation of acetylenic ketone and formaldehyde in the 4-butynediols process is characterized in that closing N after temperature rises to 80～95 ℃
2, feed acetylene gas and carry out the generation of acetylenic ketone and the ethynylation of formaldehyde.
10, according to claim 7 is that the molecular sieve composite oxide catalyst of carrier is applied to formaldehyde ethinylation synthetic 1 with HZSM-5, the method of the ethynylation of the generation of acetylenic ketone and formaldehyde in the 4-butynediols process, it is characterized in that described catalyst amount is 2.0～6.0g catalyst/50mL formalin, the initial concentration of formalin is 15～37%%.
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|---|---|---|---|
| CN 200710008734 CN101024195A (en) | 2007-03-23 | 2007-03-23 | Method for preparing molecular sieve composite oxide catalyst using HZSM5 as carrier and its use |
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|---|---|---|---|
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| CN102125856A (en) * | 2011-01-31 | 2011-07-20 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
| CN102950014A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
| CN102950002A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for producing 1.4-butynediol and preparation method of catalyst |
| CN103157500A (en) * | 2013-03-22 | 2013-06-19 | 新疆大学 | Preparation of supported catalyst for 1,4-butynediol |
| CN105642303A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Copper bismuth catalyst for synthesis of 1, 4-butynediol and preparation method thereof |
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- 2007-03-23 CN CN 200710008734 patent/CN101024195A/en active Pending
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| CN102125856B (en) * | 2011-01-31 | 2012-11-28 | 华烁科技股份有限公司 | Supported catalyst for use in production of 1, 4-butynediol by Reppe method, preparation method thereof and application thereof |
| CN102950014A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
| CN102950002A (en) * | 2012-10-18 | 2013-03-06 | 大连瑞克科技有限公司 | Catalyst for producing 1.4-butynediol and preparation method of catalyst |
| CN102950014B (en) * | 2012-10-18 | 2014-04-16 | 大连瑞克科技有限公司 | Catalyst for production of 1,4-butynediol and preparation method of catalyst |
| CN103157500A (en) * | 2013-03-22 | 2013-06-19 | 新疆大学 | Preparation of supported catalyst for 1,4-butynediol |
| US11034713B2 (en) | 2014-06-19 | 2021-06-15 | Haldor Topsoe A/S | Crystalline microporous material mediated conversion of C1-3 oxygenate compounds to C4 oxygenate compounds |
| CN105709758B (en) * | 2014-12-04 | 2018-02-09 | 中国石油化工股份有限公司 | A kind of copper bismuth catalyst and preparation method thereof |
| CN105642303A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Copper bismuth catalyst for synthesis of 1, 4-butynediol and preparation method thereof |
| CN105709759A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of copper-bismuth catalyst for 1, 4-butynediol synthesis |
| CN105642300A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Preparation method of copper bismuth catalyst for synthesis of 1, 4-butynediol |
| CN105642303B (en) * | 2014-12-04 | 2018-02-09 | 中国石油化工股份有限公司 | Synthesize copper bismuth catalyst of 1,4 butynediols and preparation method thereof |
| CN105709759B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of copper bismuth catalyst preparation method for being used to synthesize 1,4 butynediols |
| CN105642300B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of copper bismuth catalyst preparation method for synthesizing 1,4 butynediols |
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| CN108067239A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of bulky grain copper bismuth catalyst and its preparation method and application |
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| CN111468129A (en) * | 2020-05-29 | 2020-07-31 | 山西大学 | Preparation method of nanosheet catalyst for ethynylation reaction of formaldehyde |
| CN111468129B (en) * | 2020-05-29 | 2023-03-07 | 山西大学 | Preparation method of nanosheet catalyst for ethynylation reaction of formaldehyde |
| CN112500271A (en) * | 2020-12-09 | 2021-03-16 | 南开大学 | Method for preparing acetophenone compounds by catalyzing phenylacetylene with molecular sieve |
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