CN112023963B - 一种1 ,4-丁炔二醇合成催化剂及应用 - Google Patents
一种1 ,4-丁炔二醇合成催化剂及应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims description 14
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 10
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 10
- 210000003278 egg shell Anatomy 0.000 claims abstract description 10
- 229940036348 bismuth carbonate Drugs 0.000 claims abstract description 7
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 7
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 7
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims abstract description 4
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 24
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 12
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- 239000011259 mixed solution Substances 0.000 claims 4
- 238000002156 mixing Methods 0.000 claims 3
- 238000005303 weighing Methods 0.000 claims 1
- KBZSNAZVDVIXKL-UHFFFAOYSA-L bismuth copper carbonate Chemical compound [Cu+2].[Bi+3].[O-]C([O-])=O KBZSNAZVDVIXKL-UHFFFAOYSA-L 0.000 abstract description 14
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 238000011156 evaluation Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000005905 alkynylation reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- -1 acetylene aldehyde Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- UTDFEXXDUZZCQQ-UHFFFAOYSA-N copper;oxobismuth Chemical compound [Cu].[Bi]=O UTDFEXXDUZZCQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Abstract
一种1,4‑丁炔二醇合成催化剂及应用,其属于工业催化的技术领域。该催化剂以微米级α‑氧化铝为载体,采用质量百分比含量为10%~50%的氧化铝为载体,以沉积沉淀法、共浸渍法等方法把碱式碳酸铜和碱式碳酸铋负载到载体上,使催化剂颗粒具有蛋壳型结构,载体处于核心,活性组分碱式碳酸铜和碱式碳酸铋包裹在载体外表面。催化剂含有质量20%~50%铜、2%~8%铋。该催化剂避免了现有英威达工艺1,4‑丁二醇生产过程中炔化工段炔化催化剂采用不含载体的碱式碳酸铜铋催化剂不易活化、副产物高的问题。该催化剂相较于现有碱式碳酸铜铋催化剂活化时间可减少40%、活性提高20%、催化剂寿命提高50%以上。
Description
技术领域
本发明属于催化剂技术领域,具体涉及一种新型合成1,4-丁炔二醇的炔化催化剂及其应用,主要应用于采用英威达Reppe法生产1 ,4-丁二醇工艺过程中1 ,4-丁炔二醇的合成,但不限于该技术的应用。
背景技术
国内外用于炔醛法(Reppe法)生产1,4-丁炔二醇的生产工艺包括英威达工艺、I.S.P工艺、F-T工艺和国内的三维工艺等,其中英威达工艺采用不含载体的碱式碳酸铜铋作为催化剂,目前催化剂的供应商为美国领先公司,国内也对该催化剂进行了研究,专利CN105642300A、CN105642301A、CN105642303A、CN106669691A、CN106669697A等均对无载体的碱式碳酸铜铋催化剂进行了研究; I.S.P工艺、F-T工艺和国内的三维工艺等采用的催化剂为硅酸镁载体负载氧化铜、氧化铋的催化剂,目前主要的催化剂供应商为德国的巴斯夫公司,专利CN107952443A、CN103638937A、CN102950014A等对以硅酸镁为载体的催化剂进行了研究。
由于各种工艺特点的不同,上述以碳酸铜铋催化剂与以硅酸镁为载体的氧化铜铋催化剂不能够在不同的工艺当中混用,碱式碳酸铜铋催化剂由于不含有载体且颗粒较大,催化剂在使用过程中,催化剂的活化操作繁琐,容易造成催化剂的失活,活化后的催化剂由于具有较大的颗粒度,反应物进出催化剂颗粒内部困难,副反应多,严重影响了催化剂的过滤性能,英威达工艺中催化剂的寿命仅为2个月左右,给1,4-丁二醇的生成带来了很大的困难。
为了解决现有装置的催化剂寿命短的问题,需要在碱式碳酸铜铋的基础之上,引入催化剂的载体,提高催化剂的耐磨性能,提高催化剂的使用寿命。
发明内容
选用α-Al2O3作为催化剂载体,该载体在pH值2-10范围内不流失,可完全满足催化剂在pH值4-7范围内使用的需要。
本发明采用的技术方案为:一种1 ,4-丁炔二醇合成催化剂及应用,该催化剂以微米级α-氧化铝为载体,采用质量百分比含量为10%~60%的氧化铝为载体,以沉积沉淀法、共浸渍法等把碱式碳酸铜和碱式碳酸铋负载到载体上,使催化剂颗粒具有蛋壳型结构,载体处于核心,活性组分碱式碳酸铜和碱式碳酸铋包裹在载体外表面。催化剂含有质量20%~50%铜、2%~8%铋。该催化剂应用于采用英威达Reppe法生产1 ,4-丁二醇工艺过程中1,4-丁炔二醇的合成。
上述该催化剂的颗粒直径为5 ~ 80μm,载体颗粒直径为1 ~ 50μm,比表面积小于30m2/g,所述的载体为α-氧化铝,氧化铝中α晶相含量大于40%。
催化剂的制备方法为沉积沉淀法、共浸渍法等催化剂制备方法,但不限于以上的制备方法。
催化剂颗粒结构为蛋壳型,载体处于核心,活性组分碱式碳酸铜和碱式碳酸铋包裹在载体外表面。
催化剂主要应用于采用英威达Reppe法生产1 ,4-丁二醇工艺过程中1 ,4-丁炔二醇的合成,但不限于该技术的应用。
本发明的有益效果:现有碱式碳酸铜铋催化剂由于不含有载体且颗粒较大,催化剂在使用过程中,催化剂的活化操作繁琐,容易造成催化剂的失活,活化后的催化剂由于具有较大的颗粒度,反应物进出催化剂颗粒内部困难,副反应多,严重影响了催化剂的过滤性能。与现有碱式碳酸铜铋催化剂相比,该催化剂中含有α-Al2O3作为催化剂载体,经过处理后该载体在pH值2-10范围内不流失,可完全满足催化剂在pH值4-7范围内使用的需要。并且以α-Al2O3作为催化剂载体,可以缩短催化剂活化的时间,活化时间可减少40%。现有的英威达工艺中催化剂的寿命仅为60天左右,本申请中引入催化剂的载体,提高催化剂的耐磨性能,其使用寿命可以达到90天以上,催化剂寿命提高50%以上。从催化剂的催化活性看,现有催化剂的甲醛转化率为71.55%,本申请中催化剂甲醛转化率为85.47%以上,催化活性提高了20%以上。
催化剂的结构为蛋壳型,活性组分铜铋包覆在载体外表面,外部蛋壳为包覆的活性组分碱式碳酸铜铋,内部核心为催化剂载体。
附图说明
图1是实施例1中催化剂BYD-1的电镜扫描图。
图2是单个催化剂颗粒的微观结构。
图3是蛋壳结构的微观示意图。
具体实施方式
实施例1
取α-氧化铝载体40g,平均颗粒度为15μm,加入到反应釜内并加入200g水,保持60℃,取500ml 1mol/L的硝酸铜溶液,其中硝酸铋浓度为6g/L,用蠕动泵将50ml的硝酸铜溶液加入到载体浆料当中,搅拌10分钟,接着加入1mol/L的碳酸钠溶液调节pH到7.0;然后再加入50ml的硝酸铜搅拌10分钟,接着加入1mol/L的碳酸钠溶液调节pH到7.0,如此反复10次将500ml硝酸铜全部加入,调节到pH为7.0,过滤洗涤,烘干,即得成品催化剂。催化剂的平均颗粒度为26μm。编号为BYD-1,催化剂评价评价结果见表1.
实施例2
取α-氧化铝载体40g,平均颗粒度为8μm,加入到反应釜内并加入200g水,取500ml1mol/L的硝酸铜溶液,其中硝酸铋浓度为6g/L,用蠕动泵将50ml的硝酸铜溶液加入到载体浆料当中,搅拌10分钟,接着加入1mol/L的碳酸钠溶液调节pH到7.0;然后再加入50ml的硝酸铜搅拌10分钟,接着加入1mol/L的碳酸钠溶液调节pH到7.0,如此反复10次将500ml硝酸铜全部加入,调节到pH为7.0,过滤洗涤,烘,即得成品催化剂。催化剂的平均颗粒度为15μm。编号为BYD-2,催化剂评价结果见表1.
实施例3
取α-氧化铝载体40g,平均颗粒度为8μm,加入到反应釜内并加入200g水,取500ml1mol/L的硝酸铜溶液,其中硝酸铋浓度为6g/L,取足量的1mol/L的碳酸钠溶液, 保持pH为7.0-7.2之间,用蠕动泵并流向载体浆料中加入硝酸铜溶液和碳酸钠溶液,加料时间为2h,将500ml硝酸铜全部加入,然后搅拌1h,过滤洗涤,烘干,即得成品催化剂。催化剂的平均颗粒度为15.5μm。编号为BYD-3,催化剂评价结果见表1.
实施例4
取α-氧化铝载体40g,平均颗粒度为8μm,配制4mol/L的硝酸铜溶液125ml,其中硝酸铋浓度为25g/L,取25ml溶液与40g载体混合均匀,在搅动状态下加入130ml的10%碳酸钠溶液,然后浆料在120度下烘干,得到粉末1;粉末1再前述含有硝酸铋的25ml硝酸铜混合,在搅动状态下加入130ml的10%碳酸钠溶液,然后浆料在120度下烘干,得到粉末2;如此反复,加入所有125ml硝酸铜溶液,得到粉末5,粉末5用去离子水洗涤到水的电导率为50-100ms/um,然后在120℃下烘干,得到催化剂粉末。催化剂的平均颗粒度为15.1μm。编号为BYD-4,催化剂评价结果见表1.
制备的催化剂采用如下评价方法考察催化剂的性能:
三口烧瓶中加入10g催化剂,加入37%甲醛150ml,以5L/h的速度通入20%C2H2-N2气体,升温到80℃,保持10h,然后升温到90℃反应7h,反应过程用10%碳酸钠溶液调节反应液的pH值在5.0-5.5之间,降温分析甲醛转化率及丁炔二醇选择性。
催化剂评价结果如表1:
从催化剂的评价结果看,采用α-氧化铝载体制备的蛋壳型碱式碳酸铜铋炔化催化剂的活性、选择性均优于现有工业无载体铜铋催化剂的性能。
从图1到图3中可以看出,催化剂的结构为蛋壳型,活性组分铜铋包覆在载体外表面,外部蛋壳为包覆的活性组分碱式碳酸铜铋,内部核心为催化剂载体。由于活性组分处于催化剂颗粒的外表面,反应时反应物容易进入活性中心部位,反应产物容易脱离活性中心离开催化剂,这样加快了反应速率。同时反应物在催化剂表面停留时间较短,发生副反应的几率较小,提高了催化剂的选择性。
平均颗粒度的分析:对活化之后的催化剂采用激光粒度仪进行催化剂粒度的分析,由于制备催化剂为蛋壳型结构,活性中心处于催化剂的外表面,平均颗粒度的大小对催化剂活性影响不大,但相对于无载体的催化剂,催化剂活性明显提高。
现有的英威达工艺中催化剂的寿命仅为60天左右,本申请中引入催化剂的载体,提高催化剂的耐磨性能,其使用寿命可以达到90天左右,催化剂寿命提高50%以上。从催化剂的催化活性看,现有催化剂的甲醛转化率为71.55%,本申请中催化剂甲醛转化率为85.47%以上,催化活性提高了20%以上。该催化剂避免了现有英威达工艺1,4-丁二醇生产过程中炔化工段炔化催化剂采用不含载体的碱式碳酸铜铋催化剂不易活化、副产物高的问题。该催化剂相较于现有碱式碳酸铜铋催化剂活化时间可减少40%、活性提高20%、催化剂寿命提高50%以上。
Claims (3)
1. 一种1 ,4-丁炔二醇合成催化剂,其特征在于:该催化剂以微米级α-氧化铝为载体,其特征在于:催化剂中含有质量百分比20%~50%铜、2%~8%铋,余量为载体α-氧化铝;所述载体α-氧化铝中α晶相含量大于40%;所述载体颗粒直径为1 ~ 50μm,比表面积小于30m2/g;
以沉积沉淀法或共浸渍法把碱式碳酸铜和碱式碳酸铋负载到载体上,使催化剂颗粒具有蛋壳型结构,载体处于核心,活性组分碱式碳酸铜和碱式碳酸铋包裹在载体外表面;所述催化剂的颗粒直径为5 ~ 80μm。
2.根据权利要求1 所述的一种1 ,4-丁炔二醇合成催化剂的制备方法,其特征在于:
催化剂的制备方法为沉积沉淀法采用以下步骤:
取α-氧化铝载体加入到反应釜内,并加入水,取硝酸铜与硝酸铋混合溶液,加入的1mol/L的碳酸钠溶液, 保持pH为7.0-7.2之间,全部加入后搅拌1h,过滤洗涤,烘干,即得成品催化剂;硝酸铜和硝酸铋混合溶液中,硝酸铜的浓度为1-5mol/L,硝酸铋的浓度为5-25g/L,催化剂粉末中含有质量百分比20%~50%铜、2%~8%铋;
催化剂的制备方法为共浸渍法采用以下步骤:
配制硝酸铜和硝酸铋混合溶液5-10份,称取α-氧化铝载体;取一份溶液与载体混合均匀,在搅动状态下加入10%碳酸钠溶液,将浆料在120℃下烘干,得到粉末;取另一份溶液与前一步得到的粉末混合均匀,在搅动状态下加入10%碳酸钠溶液,将浆料在120℃下烘干,再得到粉末;重复以上操作,直到与所有溶液混合完成,得到最终催化剂粉末;所述硝酸铜和硝酸铋混合溶液中,硝酸铜的浓度为1-5mol/L,硝酸铋的浓度为5-25g/L,催化剂粉末中含有质量百分比20%~50%铜、2%~8%铋。
3.根据权利要求1 所述的一种1 ,4-丁炔二醇合成催化剂的应用,其特征在于:该催化剂应用于采用英威达Reppe法生产1 ,4-丁二醇工艺过程中1 ,4-丁炔二醇的合成。
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