CN112934250A - 一种腈加氢催化剂和制备及应用 - Google Patents
一种腈加氢催化剂和制备及应用 Download PDFInfo
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 12
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
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- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium 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
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
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- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 235000003893 Prunus dulcis var amara Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
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- 239000013556 antirust agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
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- 235000002867 manganese chloride Nutrition 0.000 description 1
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- 239000011733 molybdenum Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
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- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
本发明公开了一种腈加氢催化剂的制备方法及应用。制备方法包括，用全硅分子筛与硅溶胶溶液按比例混捏、造粒和热处理得到载体，在载体上按比例负载金属活性组分和助剂，经过干燥、焙烧和还原得到目标催化剂。采用本发明方法制备的催化剂在固定床连续加氢制备间苯二甲胺反应中具有更高的活性和间苯二甲胺收率。解决了现有间歇釜式技术中催化剂易于失活和产品选择性低等问题，具有良好的工业应用前景。
Description
技术领域
本发明涉及一种腈加氢催化剂的制备方法及应用。
背景技术
间苯二甲胺常温下是一种无色、具有苦杏仁味的液体，是一种重要的精细化工原料。主要用于生产特种塑料和油漆，还可用于合成农药、防锈剂、橡胶助剂、润滑剂、纸加工剂等。
间苯二甲胺是通过间苯二甲腈液相加氢制得，反应工艺主要以釜式间歇加氢和固定床连续加氢为主。由于原料间苯二甲腈在常温下溶解度较低，寻找合适的溶剂或者进料工艺及与工艺相匹配的催化剂是一个重要的研究内容。CN2011110070427.5介绍了一种高压釜式间歇加氢制备间苯二甲胺的工艺，该工艺使用改性骨架镍催化剂，甲苯为溶剂，间苯二甲胺收率大于94％，催化剂可以套用10次。但甲苯对间苯二甲腈的溶解度较低，只能使用间歇釜工艺，限制了其规模化连续生产。CN200910249508.4公开了一种制备苯二甲胺的方法，使用的是负载型镍或钴催化剂，可用于间歇釜式连续加氢工艺，间苯二甲胺摩尔收率可以达到90％。但该工艺仍然是间歇釜式反应且间苯二甲胺收率不高。CN201110072099.2公开了一种在临氨条件下固定床加氢制间苯二甲胺的方法，使用的是助剂改性的负载型镍或钴催化剂，间苯二甲胺收率达到97％。但反应结果中出现间苯二甲腈和间甲胺基苯甲腈未完全反应的现象，说明单活性组分催化剂活性不高。CN201310180022.6公开了一种固定床连续加氢制备间苯二甲胺的方法，该工艺选用碱性助剂改性的镍催化剂，苯二甲胺收率可以达到96％，但该方法没有介绍使用的溶剂及间苯二甲腈溶液的溶解度，无法确定原料的空速。
发明内容
本发明的目的在于针对上述问题，提供适用于固定床连续加氢制备间苯二甲胺催化剂的制备方法。
本发明的目的可以通过以下方式实现：
全硅分子筛与硅溶胶溶液按比例混捏、造粒和热处理得到载体，在载体上按比例负载金属活性组分和助剂，经过干燥、焙烧和还原得到目标催化剂。制备催化剂包括以下步骤：
(1)用全硅分子筛与硅溶胶溶液按比例混捏，全硅分子筛的比例为10％-85wt.％，用造粒机处理成适合反应器大小的载体，在300-600℃条件下焙烧1-24h。
(2)将步骤(1)中焙烧后的载体负载Ni和Co活性组分及助剂，控制活性组分含量10％-30％，Ni/Co(质量比)＝0.5-3，助剂含量为0-10wt.％。经干燥和焙烧后，在200-550℃氢气还原1-8h得到目标催化剂。
上述制备催化剂的步骤(1)所述全硅分子筛为全硅MCM-41、MCM-22、SBA-15中的一种或者二种。硅溶胶溶液中的二氧化硅浓度为10％-40％。
步骤(2)所述活性组分及助剂负载过程采用的金属源为其可溶性硝酸盐、醋酸盐、氯化盐、硫酸盐、草酸盐、葡萄糖酸盐、柠檬酸盐、苯甲酸盐、溴化盐的一种或任意二种以上。所述的助剂为Mn、Cu、Sn、Cr、Fe、Mo中的一种或任意二种以上。
步骤(2)所述的催化剂制备方法为浸渍法、沉淀法、离子交换法和水热合成法中的一种或二种以上结合。
步骤(2)所述的催化剂应用于固定床间苯二甲腈溶液连续加氢反应。加氢反应所用的溶剂为甲苯/甲醇＝1:4-4:1、丁醇、液氨、苯二甲胺中的一种或任意二种以上。原料间苯二甲腈溶液的溶解度为5-15wt.％。加氢反应温度为50-180℃，优选反应温度为70-150℃；反应压力为4-12MPa，优选反应压力为6-10MPa；反应体积空速为0.1-5h-1，优选反应体积空速为0.3-2h-1；氢气与间苯二甲腈摩尔比为5-65，优选摩尔比为15-50。
采用本发明方法制备的催化剂在连续加氢制备间苯二甲胺反应中具有更稳定的活性和间苯二甲胺收率。解决了现有技术中催化剂易于失活和产品选择性低等问题，具有良好的工业应用前景。
具体实施方式
以下的实施例对本发明做进一步的说明，但本发明并不局限于以下的实施例。尽管参照一下实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解，其依然可以对下述各实施例所表述的技术方案进行修改，或者对其中部分特征进行等同替换，而这些修改或替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
催化剂制备
载体一
50g MCM-41分子筛和40g 25％硅溶胶混捏1h，晾干后用造粒机处理成20-40目颗粒。经过120℃烘干4h和300℃焙烧4h后备用。载体的比表面积和孔体积分别为573m2/g和0.85cm3/g。
载体二
50g MCM-22分子筛和45g 40％硅溶胶混捏1h，晾干后用造粒机处理成20-40目颗粒。经过120℃烘干4h和400℃焙烧4h后备用。载体的比表面积和孔体积分别为428m2/g和0.52cm3/g。
催化剂一
40mL去离子水中加入一定量的硝酸镍、醋酸钴、氯化铁，溶液中镍、钴和铁的质量分别为6g、3.5g和0.5g，Ni/Co(质量比)＝1.7，搅拌均匀后浸渍到40g载体一上，经过120℃烘干4h和400℃焙烧4h和400℃H2还原2h制得12％Ni-7％Co-1％Fe/MCM-41-SiO2催化剂(质量分数)。
催化剂二
40mL去离子水中加入一定量的乙酸镍、硝酸钴，溶液中镍和钴的质量分别为12g和4g，Ni/Co(质量比)＝3，搅拌均匀后浸渍到40g载体一上，经过120℃烘干2h、400℃焙烧3h和400℃H2还原4h制得21.4％Ni-7.1％Co/MCM-41-SiO2催化剂(质量分数)。
催化剂三
40mL去离子水中加入一定量的草酸镍、硝酸钴和二氯化锡，溶液中镍、钴和锡的质量分别为10g、3.7g和0.3g，Ni/Co(质量比)＝2.7，搅拌均匀后浸渍到40g载体一上，经过120℃烘干2h、500℃焙烧4h和400℃H2还原3h制得18.5％Ni-6.9％Co-0.6％Sn/MCM-41-SiO2催化剂(质量分数)。
催化剂四
40mL去离子水中加入一定量的氯化镍、氯化钴和氯化锰，溶液中镍、钴和锰的质量分别为3.5g、7g和0.5g，Ni/Co(质量比)＝0.5，搅拌均匀后浸渍到上述载体上，经过120℃烘干2h、400℃焙烧2h和400℃H2还原2h制得6.9％Ni-13.7％Co-1％Mn/MCM-41-SiO2催化剂(质量分数)。
催化剂五
40mL去离子水中加入一定量的柠檬酸镍、草酸钴和硝酸铬，溶液中镍、钴和铬的质量分别为5g、4.5g和0.2g，Ni/Co(质量比)＝1.1，搅拌均匀后浸渍到40g载体一上，经过120℃烘干2h、500℃焙烧3h和550℃H2还原2h制得10.1％Ni-9.1％Co-0.4％Cr/MCM-41-SiO2催化剂(质量分数)。
催化剂六
40mL去离子水中加入一定量的硝酸镍、醋酸钴和钼酸铵，溶液中镍、钴和钼的质量分别为6.5g、3.5g和0.05g，Ni/Co(质量比)＝1.86，搅拌均匀后浸渍到40g载体一上，经过120℃烘干2h、500℃焙烧3h和550℃H2还原2h制得13％Ni-7％Co-0.1％Mo/MCM-41-SiO2催化剂(质量分数)。
催化剂七至十二
将催化剂一至六的载体换成载体二，其他制备条件不变。
对比例1
40mL去离子水中加入一定量的硝酸镍、醋酸钴、氯化铁，溶液中镍、钴和铁的质量分别为6g、3.5g和0.7g，Ni/Co(质量比)＝1.7，搅拌均匀后浸渍到40g商品球形二氧化硅载体上，载体的比表面积和孔体积分别为211m2/g和0.53cm3/g。经过120℃烘干4h和400℃焙烧4h和400℃H2还原2h制得12％Ni-7％Co-1.4％Fe/SiO2催化剂(质量分数)。
对比例2
40mL去离子水中加入一定量的乙酸镍、硝酸钴，溶液中镍和钴的质量分别为12g和4g，Ni/Co(质量比)＝3，搅拌均匀后浸渍到40g用25％硅溶胶焙烧制得的块状硅胶载体上，载体的比表面积和孔体积分别为176m2/g和0.48cm3/g。经过120℃烘干2h、400℃焙烧3h和400℃H2还原4h制得21.4％Ni-7.1％Co/SiO2催化剂(质量分数)。
实施例1
本实施例使用液氨88wt.％和间苯二甲胺2wt.％作为溶剂，25℃配置溶解度10wt.％间苯二甲腈溶液。使用固定床反应器，上述催化剂装填量为3.5g，反应温度90℃，反应压力8MPa，体积空速3.5h-1，氢气/间苯二甲腈(摩尔比)＝50。反应后经过分离后使用气相色谱定量分析，结果见表1。
表1加氢制间苯二甲胺反应结果
| 催化剂 | 间苯二甲腈转化率(％) | 间苯二甲胺选择性(％) |
| 1 | 100 | 95.1 |
| 2 | 100 | 97.8 |
| 3 | 100 | 95.3 |
| 4 | 100 | 95.1 |
| 5 | 100 | 93.2 |
| 6 | 100 | 96.5 |
| 7 | 100 | 97.2 |
| 8 | 100 | 98.1 |
| 9 | 100 | 97.0 |
| 10 | 100 | 92.1 |
| 11 | 100 | 97.2 |
| 12 | 100 | 97.4 |
| 对比例1 | 100 | 91.2 |
| 对比例2 | 100 | 92.7 |
结果表明：用自制的复合载体制备的双金属组分加氢催化剂在固定床间苯二甲腈加氢反应中比其他载体制备的催化剂加氢选择性高，具有良好的工业应用前景。
Claims (8)
1.一种腈加氢催化剂的制备方法，其特征在于：
1)用全硅分子筛与硅溶胶溶液混捏、造粒制成载体，载体中全硅分子筛的比例为10wt.％-85wt.％(优选15wt.％-75wt.％)，在200-700℃(优选300-600℃)条件下焙烧1-24h(优选2-18h)；
2)将步骤(1)的载体负载Ni和Co活性组分，其中含有或不含有助剂，控制催化剂中活性组分含量10wt.％-40wt.％(优选12wt.％-30wt.％)，Ni/Co(质量比)＝0.3-4(优选0.5-3)，催化剂中助剂含量为0-10wt.％(优选0-6wt.％)；经干燥，在200-700℃(优选300-600℃)条件下焙烧1-24h(优选2-18h)，在200-600℃(优选300-550℃)氢气还原1-6h(优选2-5h)得到目标催化剂。
2.按照权利要求1所述的方法，其特征在于：步骤(1)所述的全硅分子筛为全硅MCM-41、MCM-22、SBA-15中的一种或者二种以上，硅溶胶溶液中的二氧化硅质量浓度为5％-50％(优选10％-40％)。
3.按照权利要求1所述的方法，其特征在于：
步骤(2)所述的助剂为Mn、Cu、Sn、Cr、Fe、Mo中的一种或任意二种以上。
4.按照权利要求1或4所述的方法，其特征在于：步骤(2)所述活性组分及助剂负载过程采用的金属源为其可溶性硝酸盐、醋酸盐、氯化盐、硫酸盐、草酸盐、葡萄糖酸盐、柠檬酸盐、苯甲酸盐、溴化盐的一种或任意二种以上。
5.一种权利要求1-5任一所述方法制备获得的催化剂。
6.一种权利要求6所述催化剂在间苯二甲腈溶液固定床连续加氢反应中的应用。
7.按照权利要求7所述的应用，其特征在于：所述的间苯二甲腈溶液的溶剂为体积比甲苯/甲醇＝1:4-4:1、丁醇、液氨、苯二甲胺中的一种或任意二种以上；所述的间苯二甲腈溶液的浓度为2-20wt.％(优选5-15wt.％)。
8.按照权利要求7或8所述的应用，其特征在于：所述的加氢反应的反应温度为50-180℃，优选反应温度为70-140℃；反应压力为4-12MPa，优选反应压力为6-10MPa；反应体积空速为0.1-5h-1，优选反应体积空速为0.5-4h-1；氢气与间苯二甲腈摩尔比为5-65，优选摩尔比为15-50。
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