CN109622039A - 一种制备1,4-丁炔二醇的方法 - Google Patents
一种制备1,4-丁炔二醇的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 21
- JSPXPZKDILSYNN-UHFFFAOYSA-N but-1-yne-1,4-diol Chemical class OCCC#CO JSPXPZKDILSYNN-UHFFFAOYSA-N 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 31
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000013049 sediment Substances 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001621 bismuth Chemical class 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
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- 229910002651 NO3 Inorganic materials 0.000 claims description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
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- 230000000274 adsorptive effect Effects 0.000 abstract description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 description 3
- BBGINXZYXBFSEW-UHFFFAOYSA-N [Cu].C#C Chemical compound [Cu].C#C BBGINXZYXBFSEW-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- 239000012043 crude product Substances 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 239000000391 magnesium silicate Substances 0.000 description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 description 2
- 235000019792 magnesium silicate Nutrition 0.000 description 2
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WKULXWGYZFXFLJ-UHFFFAOYSA-N [Cu]=CC=[Cu] Chemical compound [Cu]=CC=[Cu] WKULXWGYZFXFLJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 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
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 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 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- -1 that is Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/391—Physical properties of the active metal ingredient
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明涉及一种制备1,4‑丁炔二醇的方法,将乙炔与甲醛水溶液进行反应,以在Cu‑Bi/ZIF‑8催化剂为催化剂,由于ZIF‑8具有较高的比表面积,可控的孔道结构,而且所制备的混杂材料是二元金属的ZIFs材料,克服了表面吸附强度与吸附选择性不高的缺陷,提高了活性组分Cu‑Bi的分散程度和固载强度,使得催化剂具有良好的活性和稳定性具有尺寸均一,形貌规整,催化剂的耐磨性及稳定性好、活性组分不容易流失;使用本发明的催化剂,乙炔的转化率高达98%以上,1,4‑丁炔二醇的选择性在95%以上,且催化可连续使用380小时以上无需更换。
Description
技术领域
本发明涉及化工生产技术领域,具体涉及一种制备1,4-丁炔二醇的方法。
背景技术
1,4-丁炔二醇(C4H6O2),白色斜方结晶,可溶于水、酸、乙醇和丙酮,不溶于苯、乙醚,对眼部粘膜、皮肤和上呼吸道有刺激作用。可用于制备丁烯二醇、丁二醇、正丁醇、二氢呋喃、四氢呋喃等一系列重要的有机化工产品,还可用作电镀光亮剂。在工业上,1,4-丁炔二醇的主要生产方法为 Reppe法:即乙炔在铜催化剂的作用下和一个分子甲醛加成,生成丙炔醇,后者再与一个甲醛分子加成,生成1,4-丁炔二醇。反应过程中催化剂采用铜作为主要活性组分,以铋作为助催化剂即铜催化剂,主要成分为 CuO-Bi2O3,(Cu含量约20%,Bi含量约2~3%)。反应前,在反应釜内,加入铜催化剂(CuO-Bi2O3),和25~35%甲醛溶液,在温度为60~100℃,通入0.10~0.15MPa的乙炔气体进行活化,8~12h后,使活性组分铜转化为乙炔铜,得到乙炔铜/铋催化剂。然后再连续加入甲醛溶液和乙炔,控制反应釜内压力为0.05~0.15MPa,温度为80~100℃,使甲醛与乙炔在乙炔铜/铋催化剂的作用下进行反应得到1,4-丁炔二醇粗品,反应料液再经反应釜内的袋式过滤器进行过滤,滤出液1,4-丁炔二醇粗品经浓缩精制得到成品。该制备方法,在反应过程中,随着反应时间的增加,催化剂乙炔铜/铋的活性会降低,1,4-丁炔二醇的收率也会降低,一般反应3~6个月后,催化剂乙炔铜/铋的活性会彻底丧失,此时需要停车更换新的催化剂。
US4110249和US4584418以及CN1118342A分别公开了以无载体的孔雀石,无载体氧化铜/氧化铋催化剂,这些催化剂不耐磨,金属组份容易流失。
US3920759和CN102125856A分别公开了以硅酸镁、高岭土为载体的铜铋负载型催化剂,用于甲醛和乙炔反应合成1,4-丁炔二醇的催化反应。但该类催化剂存在以下不足:
(1)载体硅酸镁不稳定,在反应体系中会发生溶解,寿命短;(2)催化剂用量多,金属氧化铜含量较高,易发生团聚,不能充分发挥每个活性中心的催化效果,造成铜资源的浪费。
CN201210157882.3公开了一种铜铋催化剂及制备方法,其步骤如下:采用有机硅源的醇溶液滴加到含有铜盐、铋盐、镁盐和分散剂的混合液中,用碱溶液调节混合溶液的pH值得到混合沉淀物,经进一步老化、采用分散剂为介质进行沉淀物的洗涤,并采用惰性气氛进行焙烧。该催化剂的活性较高,但是成本较高、机械强度差,难于实现工业化。
CN201210397161.X公开了用于1,4-丁炔二醇生产的催化剂及其制备方法,该方法采用纳米二氧化硅为载体,以沉淀沉积的方法,将铜和铋吸附在载体上。此方法制备的催化剂具有较好的活性和选择性,但是由于采用尿素为沉淀剂,反应过程较慢,会产生大量的氨气,造成环境污染,而且制备的催化剂颗粒较小,不好过滤。
CN103170342A公开了一种合成1,4-丁炔二醇的纳米CuO-Bi2O3催化剂,其特征在于,将适量表面活性剂和氢氧化钠溶液分别加入铜铋酸性水溶液中,在一定温度下热解制备纳米催化剂。所制备的催化剂颗粒大小 10~80nm。该催化剂反应活性较高,但由于催化剂的颗粒小,用于淤浆床或者悬浮床,颗粒小,难过滤。而且纳米CuO-Bi2O3活性中心暴露多,容易失活。
综上所述,现有技术中生产1,4-丁炔二醇的催化剂普遍存在着催化剂颗粒度不适中、催化剂的耐磨性及稳定性差、活性组分容易流失等技术问题。
发明内容
针对现有技术的不足,本发明提供一种制备1,4-丁炔二醇的方法。
本发明的目的可以通过以下技术方案来实现:
向反应釜内连续通入乙炔气体,乙炔空速为4~5min-1,连续加入质量分数25%~35%的甲醛溶液,控制反应釜内压力为0.05~0.15MPa,温度为 80~100℃,乙炔和甲醛在Cu-Bi/ZIF-8催化剂的作用下反应得到1,4-丁炔二醇;
所述Cu-Bi/ZIF-8催化剂的组成按氧化物的质量百分数计算为: CuO18.0~60%,Bi2O32~10%,余量为ZIF-8。
所述催化剂的制备方法包含如下步骤:
S1:将硝酸锌和2-甲基咪唑溶解于甲醇中,将表面活性剂溶解于上述溶液中,配置成质量浓度为1%~5%的溶液;在20~60℃搅拌反应1~6h 后静置10~18h,形成白色浑浊溶液;
S2:将步骤S1得到的浑浊溶液进行离心处理,离心分离的速度为 4000~6000rpm,时间为5~15min;将离心得到的沉淀物用甲醇洗涤3~5 次,然后将沉淀物放在烘箱中干燥,得到ZIF-8载体;
S3:将可溶性铜盐和可溶性铋盐用水溶解后浸渍在步骤S2所述的ZIF-8 载体上,浸渍时间为2~8h,负载量为1~30%;然后放入烘箱中干燥5~ 10h,温度为80~100℃;最后放入马弗炉内焙烧2~8h,温度为300~500℃,得到Cu-Bi/ZIF-8催化剂。
其中,在步骤S1中其中硝酸锌的质量浓度为1%~10%,2-甲基咪唑的质量浓度为1%~10%;所述的表面活性剂为聚乙二醇、十二烷基硫酸钠、聚乙烯吡咯烷酮中的一种。
步步骤S2中,所述的干燥时间为1~5h,温度为100~200℃
在步骤S3中,所述的可溶性铜盐和可溶性铋盐是硫酸盐和硝酸盐、醋酸盐和氯化物等可溶性盐,优选为硝酸盐。
与现有技术相比,本发明具有如下优点:
1)本发明的Cu-Bi/ZIF-8催化剂,由于ZIF-8具有较高的比表面积,可控的孔道结构,而且所制备的混杂材料是二元金属的ZIFs材料,克服了表面吸附强度与吸附选择性不高的缺陷,提高了活性组分Cu-Bi的分散程度和固载强度,使得催化剂具有良好的活性和稳定性具有尺寸均一,形貌规整,催化剂的耐磨性及稳定性好、活性组分不容易流失。
2)本发明的工艺,使用本发明的催化剂,乙炔的转化率高达98%以上,1,4-丁炔二醇的选择性在95%以上,且催化可连续使用380小时以上无需更换。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领加入域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
【实施例1】
1)催化剂的制备
S1:将硝酸锌和2-甲基咪唑溶解于甲醇中,配制成硝酸锌的质量浓度为1%,2-甲基咪唑的质量浓度为2%的溶液,将表面活性剂溶解于上述溶液中,配置成质量浓度为1%%的溶液;在30℃搅拌反应5h后静置11h,形成白色浑浊溶液;
S2:将步骤S1得到的浑浊溶液进行离心处理,离心分离的速度为 4000rpm,时间为5min;将离心得到的沉淀物用甲醇洗涤3次,然后将沉淀物放在烘箱中干燥1h,温度为100℃,得到ZIF-8载体;
S3:将氯化铜和可硝酸铋用水溶解后浸渍在步骤S2所述的ZIF-8载体上,浸渍时间为2h,负载量为1%;然后放入烘箱中干燥5h,温度为80~ 100℃;最后放入马弗炉内焙烧8h,温度为300℃,得到Cu-Bi/ZIF-8催化剂I。
2)制备1,4-丁炔二醇的方法
向反应釜中加入80g步骤S1制备的Cu-Bi/ZIF-8的催化剂,然后控制反应釜内压力为0.15MPa,温度为100℃,向反应釜内连续通入乙炔气体,乙炔空速为5min-1,连续加入质量分数35%的甲醛溶液,乙炔和甲醛在 Cu-Bi/ZIF-8催化剂的作用下反应得到1,4-丁炔二醇;经检测,乙炔的转化率高达99.1%以上,1,4-丁炔二醇的选择性在96.2%。
【实施例2】
1)催化剂的制备
S1:将硝酸锌和2-甲基咪唑溶解于甲醇中,配制成硝酸锌的质量浓度为5%,2-甲基咪唑的质量浓度为5%,将表面活性剂溶解于上述溶液中,配置成质量浓度为3%的溶液;在40℃搅拌反应4h后静置18h,形成白色浑浊溶液;
S2:将步骤S1得到的浑浊溶液进行离心处理,离心分离的速度为 5000rpm,时间为10min;将离心得到的沉淀物用甲醇洗涤4次,然后将沉淀物放在烘箱中干燥3h,温度为150℃,得到ZIF-8载体;
S3:将可溶性铜盐和可溶性铋盐用水溶解后浸渍在步骤S2所述的ZIF-8 载体上,浸渍时间为4h,负载量为20%;然后放入烘箱中干燥7h,温度为 90℃;最后放入马弗炉内焙烧4h,温度为400℃,得到Cu-Bi/ZIF-8催化剂 I。
2)制备1,4-丁炔二醇的方法
向反应釜中加入80g步骤S1制备的Cu-Bi/ZIF-8的催化剂,然后控制反应釜内压力为0.1MPa,温度为90℃,向反应釜内连续通入乙炔气体,乙炔空速为5min-1,连续加入质量分数25%的甲醛溶液,乙炔和甲醛在 Cu-Bi/ZIF-8催化剂的作用下反应得到1,4-丁炔二醇;经检测,乙炔的转化率高达99.2%以上,1,4-丁炔二醇的选择性为97.2%。
【实施例3】
1)催化剂的制备
S1:将硝酸锌和2-甲基咪唑溶解于甲醇中,配置硝酸锌的质量浓度为 10%,2-甲基咪唑的质量浓度为10%,将表面活性剂溶解于上述溶液中,配置成质量浓度为5%的溶液;在60℃搅拌反应1h后静置10h,形成白色浑浊溶液;
S2:将步骤S1得到的浑浊溶液进行离心处理,离心分离的速度为 6000rpm,时间为15min;将离心得到的沉淀物用甲醇洗涤5次,然后将沉淀物放在烘箱中干燥5h,温度为1200℃,得到ZIF-8载体;
S3:将可溶性铜盐和可溶性铋盐用水溶解后浸渍在步骤S2所述的ZIF-8 载体上,浸渍时间为8h,负载量为30%;然后放入烘箱中干燥5h,温度为 100℃;最后放入马弗炉内焙烧2h,温度为500℃,得到Cu-Bi/ZIF-8催化剂I。
2)制备1,4-丁炔二醇的方法
向反应釜中加入80g步骤S1制备的Cu-Bi/ZIF-8的催化剂,然后控制控制反应釜内压力为0.05MPa,温度为80℃,向反应釜内连续通入乙炔气体,乙炔空速为4min-1,连续加入质量分数35%的甲醛溶液,乙炔和甲醛在Cu-Bi/ZIF-8催化剂的作用下反应得到1,4-丁炔二醇;乙炔的转化率高达 97.2%,1,4-丁炔二醇的选择性在95.1%。
上述说明已经充分揭露了本发明的具体实施方式。需要指出的是,熟悉该领域的技术人员对本发明的具体实施方式所做的任何改动均不脱离本发明的权利要求书的范围。相应地,本发明的权利要求的范围也并不仅仅局限于前述具体实施方式。
Claims (6)
1.一种制备1,4-丁炔二醇的方法,包括以下步骤:
向反应釜内连续通入乙炔气体,乙炔空速为4~5min-1,连续加入质量分数25%~35%的甲醛溶液,控制反应釜内压力为0.05~0.15MPa,温度为80~100℃,乙炔和甲醛在Cu-Bi/ZIF-8催化剂的作用下反应得到1,4-丁炔二醇;
所述Cu-Bi/ZIF-8催化剂的组成按氧化物的质量百分数计算为:CuO18.0~60%,Bi2O32~10%,余量为ZIF-8。
2.根据权利要求1所述的制备1,4-丁炔二醇的方法,其特征在于:所述催化剂的制备方法包含如下步骤:
S1:将硝酸锌和2-甲基咪唑溶解于甲醇中,将表面活性剂溶解于上述溶液中,配置成质量浓度为1%~5%的溶液;在20~60℃搅拌反应1~6h后静置10~18h,形成白色浑浊溶液;
S2:将步骤S1得到的浑浊溶液进行离心处理,离心分离的速度为4000~6000rpm,时间为5~15min;将离心得到的沉淀物用甲醇洗涤3~5次,然后将沉淀物放在烘箱中干燥,得到ZIF-8载体;
S3:将可溶性铜盐和可溶性铋盐用水溶解后浸渍在步骤S2所述的ZIF-8载体上,浸渍时间为2~8h,负载量为1~30%;然后放入烘箱中干燥5~10h,温度为80~100℃;最后放入马弗炉内焙烧2~8h,温度为300~500℃,得到Cu-Bi/ZIF-8催化剂。
3.根据权利要求2所述的制备1,4-丁炔二醇的方法,其特征在于:其中,在步骤S1中硝酸锌的质量浓度为1%~10%,2-甲基咪唑的质量浓度为1%~10%。
4.根据权利要求2所述的制备1,4-丁炔二醇的方法,其特征在于:其中,在步骤S1中所述的表面活性剂为聚乙二醇、十二烷基硫酸钠、聚乙烯吡咯烷酮中的一种。
5.根据权利要求2所述的制备1,4-丁炔二醇的方法,其特征在于:在步骤S2中,所述的干燥时间为1~5h,温度为100~200℃。
6.根据权利要求2所述的制备1,4-丁炔二醇的方法,其特征在于:在步骤S3中,所述的可溶性铜盐和可溶性铋盐是硫酸盐和硝酸盐、醋酸盐和氯化物等可溶性盐,优选为硝酸盐。
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CN114160144A (zh) * | 2021-12-16 | 2022-03-11 | 浙江联盛化学股份有限公司 | 一种无铬催化剂、其制备方法及应用 |
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