CN1145528C - 制备1,3-丙二醇的催化剂和方法 - Google Patents
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Abstract
一种固体颗粒催化剂组合物,包括一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;一种钼组分,其中钼构成催化剂组合物的5-20重量%;和10-50重量%的粘结剂材料,包括硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量不大于2重量%;和使用所述催化剂组合物将3-羟基丙醛选择性氢化成1,3-丙二醇的方法。
Description
本发明涉及1,3-丙二醇的制备。本发明一方面涉及一种将3-羟基丙醛氢化为1,3-丙二醇的改进催化剂,该催化剂在氢化反应环境中显示较长的催化剂寿命。本发明另一方面涉及一种由3-羟基丙醛制备1,3-丙二醇的改进方法。
1,3-丙二醇是聚酯制备中的一种化学中间体,可通过在水溶液中氢化3-羟基丙醛制备。3-羟基丙醛向1,3-丙二醇的选择性氢化因3-羟基丙醛的高活性和氢气在水溶液中的较低溶解性而复杂化。
小催化剂粒径有助于在滴流床构型中氢化。然而,催化剂破碎强度随催化剂粒径降低而明显变小。提高基于镍的块状催化剂的破碎强度的一种常规方法是增加粘结剂中的钙含量。然而,在含水氢化环境中,钙和其它可溶性粘结剂组分很快从催化剂中渗出。这对合成工艺存在两个不利影响。第一,随着水从1,3-丙二醇中蒸发分离出来,渗出的粘结剂材料沉积于蒸发柱内,导致停工期和装置清理费用。第二,从催化剂颗粒中除去这些可溶性组分使催化剂的破碎强度降低,导致流过催化剂床的效率降低,原因在于催化剂区域塌陷并最终堵塞床。
GB-A-1085171涉及一种用于制备含钼的硅酸镍催化剂的方法。该催化剂特别适用于由烯烃通过与一氧化碳和氢气在含氧合成中反应所得到的醛、酮和酯的含硫混合物的氢化。
GB-A-1085171寻求克服现有技术氢化催化剂所显示的问题,其中在含氧合成中同时得到的酮不能或不能理想地被氢化,并在随后对氢化反应混合物进行蒸馏时出现问题,这是因为它们与醇形成共沸混合物,所以难以从所需的醇中分离出来。
GB-A-1085171提供一种催化剂,其制备是将由水玻璃和钼酸钠制得的水溶液在0-100℃的温度下搅拌加入,其中相对于硅的摩尔是0.5-3,钠∶硅的比率为0.7∶1至7∶1,钼∶硅的比率为0.004∶1至0.2∶1,所以1-3摩尔镍钠溶液中所加入的镍量是从比与该溶液的钠含量相等的量低10重量%至高10重量%,分离从溶液得到的沉淀物,用水洗涤,并模塑,任选地在250-400℃的温度下煅烧,然后用氢气在300-500℃、优选350-400℃的温度下还原。
在GB-A-1085171中既未指出也未讨论钙和其它可溶性粘结剂组分的渗出问题以及其对催化剂破碎强度的随后影响。
因此,本发明的目的是提供一种特别用于在水溶液中将3-羟基丙醛氢化成1,3-丙二醇的催化剂和方法。具体地说,本发明的目的是提供一种用于氢化3-羟基丙醛的具有较低可渗透量的催化剂,且在反应环境中没有明显的破碎强度下降。
根据本发明,提供一种固体颗粒形式的催化剂组合物,包括(a)一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;(b)一种钼组分,其中钼构成催化剂组合物的5-20重量%;和(c)按催化剂组合物的重量计,10-50重量%的粘结剂材料,包括硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量按催化剂组合物的重量计不大于2重量%。
根据本发明。还提供一种制备1,3-丙二醇的方法,包括(a)在含水反应混合物中在至少30℃的温度下将3-羟基丙醛与氢气在固体颗粒催化剂组合物存在下接触以制备包括1,3-丙二醇的含水产物混合物,所述催化剂组合物包括(i)一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;(ii)一种钼组分,其中钼构成催化剂组合物的5-20重量%;和(iii)10-50重量%的粘结剂材料,选自硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量按催化剂组合物的重量计不大于2重量%;和(b)从含水产物混合物中回收1,3-丙二醇。
将所述催化剂用于含水3-羟基丙醛的氢化,可以高收率生产1,3-丙二醇,同时通过使用水溶性粘结剂材料缩短停工期。
下面参考附图描述本发明:
图1为本发明3-羟基丙醛氢化催化剂的催化剂活性与时间的关系图。
图2为本发明3-羟基丙醛氢化催化剂的催化剂活性与时间的关系图。
图3为常规镍氢化催化剂的催化剂活性与时间的关系图。
图4为本发明3-羟基丙醛氢化催化剂的催化剂活性与时间的关系图。
氢化催化剂含有作为主要活性组分的25-60重量%、优选25-45重量%镍(如Ni°)。活性催化剂中的镍主要是还原态。
该催化剂含有5-20重量%、优选6-16重量%钼(如Mo°)。钼以金属和氧化物形式存在于催化剂中。钼具有粘结功能,并且还是一种活性促进剂。
催化剂的粘结剂部分起到“胶”的作用以使各分离的组分固定在一起,并提供对沿催化剂床的压力降导致的破碎的抵抗力。粘结剂构成催化剂的10-50重量%,并由硅的氧化物,及硅酸盐和锌、锆、钙、镁和/或铝的氧化物构成。该催化剂通常含30-70、优选35-55重量%的硅;0-2、优选0-1重量%的锌;和0-2重量%的铝。粘结剂含不超过2重量%的钙,优选含0-1重量%的钙。催化剂的一个优选实施方案基本上不含锌或钙。用于在水溶液中将3-羟基丙醛氢化成1,3-丙二醇的优选催化剂组合物含有约35重量%的镍和约8-12重量%的钼,以及平衡量的上述粘结剂材料。
催化剂可通过将活性镍组分、钼组分和粘结剂材料掺混为固体块形式的任何工艺制备。通常催化剂制备方法包括将镍的氧化物、粘结剂材料如美国活性白土和三氧化钼粉末混合为均匀粉末。然后将胶态二氧化硅在足量水中的溶液在搅拌下掺混入固体混合物中形成可挤出混合物。接着将该湿混合物从带有直径0.10-0.18cm(0.040-0.070in)孔的模板挤出。将这些挤出物在100-125℃下干燥足够时间,以将含湿量降到低于约5重量%。然后将干燥的挤出物在450-550℃的空气中煅烧至少约3小时,直到获得所需强度。在使用前,将催化剂在氢气下在350-450℃范围内的温度下还原足够时间,以使至少60%的镍被还原。若该还原的催化剂不立即使用,则将其冷却至环境温度并在保护介质如1,3-丙二醇下贮存直至使用。说明性的催化剂制备方法提供于实施例2和3中。
催化剂为颗粒形式,其粒径和形状应根据其它工艺变量如流速和压力提供足够的催化剂活性。优选的催化剂颗粒的直径小于0.32cm(1/8in.)(沿颗粒截面宽度),优选0.08-0.16cm(1/16-1/32in.),以提供几何表面积与抗破碎强度之间的最佳平衡。对于最长的催化剂床寿命,优选的催化剂形状为三叶型(trilobal)和圆柱型。
催化剂在3-羟基丙醛向1,3-丙二醇的选择性氢化中优选显示活性至少为10h-1/催化剂体积分数,优选至少20h-1/催化剂体积分数。该催化剂在反应环境中具有改进的稳定性和在催化剂活性寿命期间的良好物理完整性。
3-羟基丙醛向1,3-丙二醇的氢化可在至少30℃、通常在50-175℃的温度下,正氢气压力至少为689kPa(100psig)、通常为1379-13790kPa(200-2000psig)下进行。HPA向PDO的氢化公开于US-5786524中。
本发明的氢化方法特别适用于通过环氧乙烷的加氢甲酰化制备1,3-丙二醇的方法,如US-A-5463145和US-A-3687981中描述的,或由丙烯醛制备1,3-丙二醇的方法,如US-A-5093537中描述的。
在该方法中,3-羟基丙醛是在水溶液中被氢化成1,3-丙二醇的中间产物。在其中一种方法中,将环氧乙烷在50-140℃温度和CO/H2压力3447-34474kPa(500-5000psig),优选60-90℃和6895-24132kPa(1000-3500psig)下在合适的加氢甲酰化催化剂如羰基钴或羰基铑存在下进行加氢甲酰化(与一氧化碳和氢气反应),生产含3-羟基丙醛、1,3-丙二醇和加氢甲酰化反应副产物的加氢甲酰化产物混合物。将3-羟基丙醛组分通过在水中萃取出来并以3-羟基丙醛浓度低于15重量%、优选低于10重量%(以水溶液的总重量计)的水溶液形式通入氢化反应器中。如上所述进行3-羟基丙醛向1,3-丙二醇的氢化,形成含1,3-丙二醇作为主产物的氢化产物混合物,将1,3-丙二醇通过合适的方式如蒸馏回收。
实施例1
常规1,3-丙二醇催化剂制备
在典型的间歇催化剂制备中,将2200份二氯化镍溶液(97-98%NiCl2)、70份Microcel E(0.8固体)和130份来自铝酸钠溶液的氧化铝投入沉淀槽中。完成沉淀后,倒出液体并将固体用去离子水洗涤数次。将固体物料(硅酸镍钙)干燥并在390-410℃下在空气中煅烧。
将730份工业级硅酸镍钙(93-97%NiCaSiAlOx)、125份MicrocelE(0.8固体)和125份膨润土粘土(0.8固体)投入3.79升(1加仑)犁-型混合器中并混合2分钟。接着,将含600份去离子水和16-20份钼(来自钼酸铵溶液)的溶液在搅拌下加入该混合物中,并继续混合5-10分钟。然后将该湿混合料从带有直径0.15-0.18cm(0.06in-0.07in)的三叶型(trilobe)孔的模板挤出。将挤出物在100-125℃下干燥过夜。然后将干燥的中间体在445-455℃下用氢气还原至被还原的镍含量约90%,按总镍量计。
实施例2
本发明的催化剂制备
将750份工业级氧化镍(93-97%NiO)、498份Attagel-30美国活性白土(0.8固体)和185份三氧化钼粉末(MoO3))投入3.79升(1加仑)犁-型混合器中并混合2-3分钟。将796份Nalco 2327(一种胶态二氧化硅溶胶,购自Nalco化学公司)在200份去离子水中的溶液在搅拌下加入该干混料中。继续搅拌5分钟。将另外的约60份去离子水加入混合器中并再搅拌5分钟。然后将该湿混合料从带有直径0.10cm(0.040英寸)孔的单celcon tri-insert挤出。将挤出物在110℃下干燥,然后分级/筛分,并在空气中在500℃下在静态陶瓷烧箱中煅烧约3小时。然后将挤出物在420-430℃下用氢气还原至被还原的镍含量约90%,按总镍量计。
实施例3
本发明的催化剂制备
将735份工业级氧化镍(93-97%NiO)、355份Attagel-30美国活性白土(0.8固体)和286份三氧化钼粉末(MoO3))投入1加仑犁-型混合器中并混合2分钟。将795份Nalco 2327胶态二氧化硅在225份去离子水中的溶液在搅拌下加入该固体混合物中,继续搅拌10分钟。然后将该湿混合料从带有直径0.10-0.18cm(0.040-0.070in)孔的模板挤出。将挤出物在100-125℃下干燥过夜。然后将该干燥的中间体在空气中在500℃下煅烧约3小时,然后用氢气在420-430℃下还原至被还原的镍含量约90%,按总镍量计。
实施例4
3-羟基丙醛的氢化
在直径3.05cm(1.2in)的滴流床反应器中进行四次氢化催化剂试验(催化剂A、B、C、D,见表1)。将400mL选取的氢化催化剂投入反应器。将该反应器用氢气加压至10342kPa(1500psig),并将已脱气的去离子水蒸汽连续加入反应器中。将自反应器放出的部分蒸汽连续返回入口并与进料一起混合,这样反应器中的表面液体流速(流入反应器的液体mL/s除以反应器的横截面积cm2)为0.3-0.8cm/s。当反应器达到所需的温度60℃时。停止加水并加入含约30%3-羟基丙醛的含水流体。通过在再循环盘管中进行热交换除去反应热。通过连续加入氢气取代消耗的气体来保持压力。定时取出原料和产物样品,并测定3-羟基丙醛的浓度。假定相对于3-羟基丙醛浓度为一级反应速率,对各原料/产物对的3-羟基丙醛浓度计算表观反应速率常数。由该反应速率常数计算催化剂对氢化3-羟基丙醛的活性,单位为液体体积/催化剂颗粒体积/时间。
在约30天内测量催化剂A至D的反应速率。催化剂C为含较低钼含量(1.8重量%)的标准现用镍氢化催化剂。催化剂A、B和D为用于在水溶液中更稳定氢化3-羟基丙醛的本发明催化剂。结果在图1-4和表1中给出。
由于反应速率主要受反应物在催化剂颗粒内的扩散速率限制,因此较小的挤出物横截面给出更有利的反应速率常数。催化剂颗粒的破碎强度随挤出物横截面尺寸的降低而降低。催化剂C太弱以致不能用0.08cm(1/32in)的孔挤出,因此用0.16cm(1/16in)孔挤出。当在催化剂中存在钙时,钙在短时间内几乎完全渗出,导致在随后的1,3-丙二醇浓缩步骤中弄脏用于蒸发水的热交换器。
表1
A0.08cm(1/32in)圆柱 | B0.08cm(1/32in)圆柱 | C0.16cm(1/16in)三叶型 | D0.16cm(1/16in)三叶型 | |||||
新制 | 38天后 | 新制 | 28天后 | 新制 | 21天后 | 新制 | 28天后 | |
NiSiAlMoCaZnFeNaLa | 35.316.21.57.80.800.60.00.4 | 37.015.91.68.00.100.500.1 | 35.514.20.912.00.700.400.1 | 未得到 | 56.94.73.51.84.60.00.50.20 | 56.96.25.21.60.20.00.60.20 | 36.015.71.380.900.500.1 | 未得到 |
破碎强度lb/mm | 2.3 | 1.3 | 3.4 | 1.7 | 1.70.9(1/32) | 1.345天后 | 5.2 | 3.1 |
平均活性 | 351 | 252 | 253 | 304 |
1见图1
2见图2
3见图3
4见图4
Claims (10)
1.一种固体颗粒形式的催化剂组合物,包括
(a)一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;
(b)一种钼组分,其中钼构成催化剂组合物的5-20重量%;和
(c)按催化剂组合物的重量计,10-50重量%的粘结剂材料,包括硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量按催化剂组合物的重量计不大于2重量%。
2.根据权利要求1的催化剂组合物,其中钼构成催化剂组合物的6-16重量%。
3.根据权利要求1或2的催化剂组合物,其中颗粒直径小于0.32cm。
4.根据权利要求1、2或3的催化剂组合物,其中镍构成催化剂组合物的25-45重量%。
5.根据前述权利要求任何一项的催化剂组合物,其中锌和钙的各自存在量按催化剂组合物的重量计不大于1重量%。
6.一种制备1,3-丙二醇的方法,包括:
(a)在含水反应混合物中在至少30℃温度下将3-羟基丙醛与氢气在固体颗粒催化剂组合物存在下接触,以制备包括1,3-丙二醇的含水产物混合物,所述催化剂组合物包括:
(i)一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;
(ii)一种钼组分,其中钼构成催化剂组合物的5-20重量%;和
(iii)按催化剂组合物的重量计,10-50重量%的粘结剂材料,包括硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量按催化剂组合物的重量计不大于2重量%;和
(b)从含水产物混合物中回收1,3-丙二醇。
7.根据权利要求6的方法,其中钼构成催化剂组合物的6-16重量%。
8.根据权利要求6或7的方法,其中固体颗粒直径小于0.32cm。
9.根据权利要求6、7或8的方法,其中在该催化剂组合物中,锌和钙的各自存在量按催化剂组合物的重量计不大于1重量%。
10.一种制备1,3-丙二醇的方法,包括:
(a)将环氧乙烷与一氧化碳和氢气在加氢甲酰化条件下并在有效量的加氢甲酰化催化剂存在下接触,形成包括3-羟基丙醛的反应产物混合物;
(b)从反应产物混合物中除去3-羟基丙醛并形成其水溶液;
(c)向该3-羟基丙醛的水溶液中加入固体颗粒氢化催化剂组合物,所述催化剂组合物包括:
(i)一种活性镍组分,其中镍构成催化剂组合物的25-60重量%;
(ii)一种钼组分,其中钼构成催化剂组合物的5-20重量%;和
(iii)按催化剂组合物的重量计,10-50重量%的粘结剂材料,包括硅的氧化物和硅酸盐及锌、铝、锆、镁和钙的氧化物中的至少一种,所述铝、钙和锌的各自存在量按催化剂组合物的重量计不大于2重量%;
(d)将该3-羟基丙醛的水溶液在正氢气压力至少为68948kPa下加热到至少30℃的温度,以制备包括1,3-丙二醇的氢化产物混合物;和
(e)从氢化产物混合物中回收1,3-丙二醇。
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US09/182,380 US5945570A (en) | 1998-10-29 | 1998-10-29 | Catalyst and process for preparing 1,3-propanediol |
US09/182,380 | 1998-10-29 |
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- 1999-10-26 BR BR9914879-0A patent/BR9914879A/pt active Search and Examination
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- 1999-10-26 EP EP99971350A patent/EP1131155B1/en not_active Expired - Lifetime
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- 1999-10-26 TR TR2001/01152T patent/TR200101152T2/xx unknown
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- 1999-10-26 JP JP2000579345A patent/JP2002528261A/ja active Pending
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KR20010082268A (ko) | 2001-08-29 |
DE69926781D1 (de) | 2005-09-22 |
CN1328487A (zh) | 2001-12-26 |
US5945570A (en) | 1999-08-31 |
NO20012088L (no) | 2001-06-26 |
AU1377300A (en) | 2000-05-22 |
ID28540A (id) | 2001-05-31 |
EP1131155A1 (en) | 2001-09-12 |
TR200101152T2 (tr) | 2001-09-21 |
MY123258A (en) | 2006-05-31 |
JP2002528261A (ja) | 2002-09-03 |
CA2348006C (en) | 2008-11-25 |
PL347502A1 (en) | 2002-04-08 |
KR100615774B1 (ko) | 2006-08-25 |
NO20012088D0 (no) | 2001-04-27 |
ATE302060T1 (de) | 2005-09-15 |
RU2232048C2 (ru) | 2004-07-10 |
EP1131155B1 (en) | 2005-08-17 |
BR9914879A (pt) | 2002-02-19 |
WO2000025914A1 (en) | 2000-05-11 |
CA2348006A1 (en) | 2000-05-11 |
US6342464B1 (en) | 2002-01-29 |
DE69926781T2 (de) | 2006-05-18 |
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