CN107684930A - 一种用于苯酚加氢制环己酮催化剂的制备方法 - Google Patents
一种用于苯酚加氢制环己酮催化剂的制备方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 33
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 24
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 88
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- 229910052796 boron Inorganic materials 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
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- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- OOJYPCDXFPWXFL-UHFFFAOYSA-N [C].OC1=CC=CC=C1 Chemical class [C].OC1=CC=CC=C1 OOJYPCDXFPWXFL-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B01J35/397—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
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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
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/646—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of aromatic or heteroaromatic rings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Abstract
一种用于苯酚加氢制环己酮催化剂的制备方法。将活性炭进行酸处理和螯合配体处理后,再进行钯吸附、碱沉淀、还原等步骤,最终得到催化剂产品。其特点是通过将活性炭进行螯合配体预处理,可利用螯合配体的给电子特性,增加Pd金属的电子密度,提高其催化加氢活性;通过在吸附液中添加氧化剂的方式,可以使金属钯均匀分布在活性炭载体的外表面,防止活性炭表面的还原基团对浸渍液中的钯离子的直接还原;通过超声波喷涂吸附技术负载活性组分,金属钯可深入活性炭表面孔内,进一步提高了Pd的分散度,有利于苯酚加氢制环己酮反应。
Description
技术领域
本发明涉及一种用于各类有机化合物加氢过程的催化剂的制备方法,特别涉及一种可将苯酚转化为环己酮的催化剂的制备方法。
背景技术
苯酚加氢制环己酮催化剂的活性、选择性和稳定性对其生产成本有较大的影响,而催化剂表面金属原子的性质、结构和数量是决定反应活性和选择性的关键。一般情况下,金属催化剂的加氢活性与金属面积大小有关,而金属面积大小与金属的晶粒度或金属的分散度有关。据报道,负载型Pd催化剂在苯酚加氢制环己酮中表现出良好的活性和选择性(GB1063357A),由于Pd是贵金属,用量一般较少,因此我们采用具有大表面积的活性炭载体将Pd高度分散,以获得大的Pd面积。由于苯酚加氢反应主要受到外扩散控制,活性组分应尽量分布于活性炭载体外表面的外部,然而,为了提高催化剂的热稳定性,也要求Pd在活性炭载体表面的分布有一定深度。这样一来,有相当部分Pd分布于活性炭孔内,也能够进一步提高Pd的分散度,增强活性炭载体作用,同时由于活性组分适当深入,外来物对催化剂的毒害也相对不易,使得活性得以保护。
活性炭作为一种有效的吸附剂,其表面物理、化学特性在吸附过程中发挥着重要的作用。其中,活性炭表面官能团很大程度上决定了活性炭对Pd金属吸附能力的强弱,此外,选择具有给电子能力的螯合配体对活性炭进行改性,可以增加Pd金属的电子密度,提高其催化加氢的活性。
传统的钯碳催化剂的制备方法为浸渍吸附法(US4394299),该方法在制备钯碳催化剂的过程中,需结合搅拌桨进行大幅度搅拌,以使钯溶液在活性炭上均匀吸附,但对于苯酚加氢制环己酮钯碳催化剂,金属钯在载体表面呈蛋壳分布,大幅度的搅拌过程容易使表面钯脱落,造成表面钯含量降低,影响催化剂的活性。而采用超声波喷涂吸附技术,一方面超声波可将吸附液打散成超微分子,深入活性炭表面孔内,进一步提高了Pd的分散度;另一方面,载体随反应器缓慢转动,均匀吸附超微分子,载体之间摩擦碰撞较轻,不易形成落粉。
发明内容
本发明的目的在于提供一种活性组分在载体表面分布均匀并具有一定深度的高性能苯酚加氢制环己酮催化剂的制备方法。
本发明的主要特点是:通过将活性炭进行螯合配体预处理,可利用螯合配体的给电子特性,增加Pd金属的电子密度,提高其催化加氢活性;通过在吸附液中添加氧化剂的方式,可以使金属钯均匀分布在活性炭载体的外表面,防止活性炭表面的还原基团对浸渍液中的钯离子的直接还原;通过超声波喷涂吸附技术负载活性组分,金属钯可深入活性炭表面孔内,进一步提高了Pd的分散度,有利于苯酚加氢制环己酮反应。
本发明提供的制备方法,它包括以下步骤:
步骤1. 将载体活性炭进行酸洗,酸液的浓度为0.1N-2.0N,温度为30℃-100℃,时间为1h-4h,水洗至中性;
步骤2. 酸洗后的活性炭再进行螯合配体吸附处理,螯合配体溶液浓度为0.01-0.3N,时间为0.5h-6h,过滤,洗涤,干燥;
步骤3. 将处理过的活性炭通过超声波喷涂吸附技术进行钯吸附,吸附液为添加有氧化剂的钯盐溶液,氧化剂与活性炭摩尔比为1:8-1:20,钯负载量为活性炭的0.05%-3%,时间为1h-12h;
步骤4. 加碱沉淀金属钯,调节pH值为8.0-10.0,沉淀时间为4h-48h,沉淀温度为30℃-90℃;
步骤5. 加入还原剂还原吸附在活性炭上的钯化合物,还原剂用量为钯离子摩尔数的50-200倍,还原温度为30℃-90℃,时间为1h-8h,过滤,洗涤,干燥。
本发明所述的活性炭选自不规则颗粒炭、规则球状炭或柱形炭。
本发明所述的酸液选自盐酸、硝酸或磷酸。
本发明所述的螯合配体选自三苯基膦、三环己基膦、三异丙叉丙酮基膦的一种或几种按任意比例组合。
本发明所述的氧化剂选自双氧水、次氯酸钠或高氯酸中的一种或几种按任意比例组合。
本发明所述的钯盐选自氯化钯或醋酸钯。
本发明所述的超声波喷涂吸附技术,吸附液用量等于活性炭饱和吸附量的40%-90%。
本发明所述的碱选自碱式碳酸盐、碳酸氢盐或碱土金属氧化物中的一种或几种按任意比例组合。
本发明所述的还原剂选自甲醛、水合肼、硼氢化钠、氢气或甲酸钠中的一种。
本发明制备的催化剂可用于苯酚加氢制环己酮反应,其方法为:将催化剂装填在反应器中,先在氢气氛围中从室温升至180℃-240℃,恒温还原6h-24h,然后降至140℃-180℃进行苯酚加氢反应,反应压力为0.05 MPa -0.3MPa,氢酚比为4/1-10/1,苯酚质量空速为0.1 h-1-0.6h-1,即得加氢产物环己酮。
本发明的有益效果为:
1.活性炭经酸处理后制备的钯碳催化剂,杂质含量低,灰分含量小。
2.酸处理后的活性炭吸附螯合配体后,可以通过电子转移增加Pd金属的电子密度,提供其催化活性,同时,螯合配体表面可以与苯酚的羟基形成O-H…P或者是O-H…п的强相互作用,使苯酚分子更容易吸附在载体表面,而一旦苯酚加氢生成环己酮,由于失去了羟基与螯合配体表面的相互作用,环己酮容易从载体表面脱附,可以防止环己酮发生过度加氢反应。
3.在钯盐溶液中加入氧化剂,可以防止钯盐直接还原,形成金属钯均匀的蛋壳形分布。
4.采用超声波喷涂吸附技术制备的钯碳催化剂,所得到的催化剂金属钯分布均匀,钯负载量为活性炭的0.05%-3%,金属钯在活性炭载体上的深入深度为50-200μm,有利于苯酚加氢制环己酮反应。
具体实施方式
实施例1
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为0.1N的盐酸溶液,100℃洗涤4h,过滤,水洗至中性;加入200mL浓度为0.01 N的三苯基磷溶液混合均匀后室温静置6h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含3mL20g/L氯化钯和2mL双氧水的混合溶液,静置1h后加入20mL水,用碳酸钠调节pH=8后,加入10mLNaHCO3,30℃下沉淀24h,加入3mL甲醛,30℃下还原8h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.49%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性95%。
实施例2
称取100g4-8目活性炭,加入500mL浓度为0.5N的盐酸溶液,100℃洗涤4h,过滤,水洗至中性;加入200mL浓度为0.02 N的三苯基磷溶液混合均匀后室温静置5h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含2mL30g/L氯化钯、1.5mL双氧水和0.3mL次氯酸钠的混合溶液,静置4h后加入20mL水,用碳酸钠调节平pH=9后,加入10mLNaHCO3,50℃下沉淀24h,升温到60℃,加入8mL甲醛还原6h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.49%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性97%。
实施例3
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为1N的盐酸溶液,80℃洗涤3h,过滤,水洗至中性;加入200mL浓度为0.1 N的三环己基膦溶液混合均匀后室温静置5h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含1.5mL40g/L氯化钯、1.5mL双氧水和0.2mL次氯酸钠的混合溶液,静置4h后加入20mL水,用碳酸钠调节pH=9后,加入10mLNaHCO3,50℃下沉淀24h,升温到60℃,加入8mlL甲醛还原6h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.51%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性92%。
实施例4
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为1N的盐酸溶液,80℃洗涤3h,过滤,水洗至中性;加入200mL浓度为0.2 N的三环己基膦溶液混合均匀后室温静置3h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含1.5mL50g/L氯化钯、1mL双氧水和0.4mL高氯酸的混合溶液,静置8h后加入20mL水,用碳酸钠调节pH=9后,加入10mLNaHCO3,70℃下沉淀24h,升温到80℃,加入10mL甲醛还原6h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为1.45%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性95%。
实施例5
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为2N的盐酸溶液,50℃洗涤2h,过滤,水洗至中性;加入200mL浓度为0.2 N的三环己基膦溶液混合均匀后室温静置3h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含1mL80g/L氯化钯、1mL双氧水和0.4mL高氯酸的混合溶液,静置8h后加入20mL水,用碳酸钠调节pH=9后,加入10mLNaHCO3,70℃下沉淀24h,升温到80℃,加入10mL甲醛还原6h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.69%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性94%。
实施例6
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为2N的盐酸溶液,30℃洗涤4h,过滤,水洗至中性;加入200mL浓度为0.3 N的三环己基膦溶液混合均匀后室温静置2h,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含1mL80g/L氯化钯、2mL双氧水和0.4mL次氯酸钠的混合溶液,静置12h后加入20mL水,用碳酸钠调节pH=9后,加入10mLNaHCO3,90℃下沉淀24h,升温到90℃,加入10mL甲醛还原8h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.65%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性90%。
对比实施例7
活性炭预处理:
称取100g4-8目活性炭,加入500mL浓度为0.1N的盐酸溶液,100℃洗涤4h,过滤,水洗至中性,过滤,洗涤,干燥后备用。
钯碳催化剂的制备:
称取10g 经过预处理的活性炭,超声波喷涂吸附含3mL20g/L氯化钯和2mL双氧水的混合溶液,静置1h后加入20mL水,用碳酸钠调节pH=8后,加入10mLNaHCO3,30℃下沉淀24h,加入3mL甲醛,30℃下还原8h,过滤,洗涤,干燥,即得本实施例的钯碳催化剂。
本实施例得到的钯碳催化剂具有下列性能:催化剂中金属钯的含量为0.49%,催化苯酚加氢制环己酮可使苯酚的转化率为99%,环己酮选择性89%。
除上述各实施例,本发明的实施方案还有很多,凡采用等同或等效替换的技术方案,均在本发明的保护范围。
尽管已在以上的举例说明中描述了本发明,但应当理解的是,所述的细节仅用于举例说明,本领域技术人员可以在不背离本发明的权利要求所限的精神和范围内对其做出变动。
Claims (9)
1.一种用于苯酚加氢制环己酮催化剂的制备方法,它包括以下步骤:
步骤1. 将载体活性炭进行酸洗,酸液的浓度为0.1N-2.0N,温度为30℃-100℃,时间为1h-4h,水洗至中性;
步骤2. 酸洗后的活性炭用含有螯合配体的溶液浸渍,使配体均匀负载在活性炭表面,螯合配体溶液浓度为0.01N-0.3N,时间为0.5h-6h,过滤,洗涤,干燥;
步骤3. 将处理过的活性炭通过超声波喷涂吸附技术进行钯吸附,吸附液为添加有氧化剂的钯盐溶液,氧化剂与活性炭摩尔比为1:8-1:20,钯负载量为活性炭的0.05%-3%,时间为1h-12h;
步骤4. 加碱沉淀金属钯,调节pH值为8.0-10.0,沉淀时间为4h-48h,沉淀温度为30℃-90℃;
步骤5. 加入还原剂还原吸附在活性炭上的钯化合物,还原剂用量为钯离子摩尔数的50-200倍,还原温度为30℃-90℃,时间为1h-8h,过滤,洗涤,干燥。
2.根据权利要求1所述的制备方法,其特征在于所述的活性炭选自不规则颗粒炭、规则球状炭或柱形炭。
3.根据权利要求1所述的制备方法,其特征在于所述的酸液选自盐酸、硝酸或磷酸。
4.根据权利要求1所述的制备方法,其特征在于所述的螯合配体选自三苯基膦、三环己基膦、三异丙叉丙酮基膦的一种或几种按任意比例组合。
5.根据权利要求1所述的制备方法,其特征在于所述的氧化剂选自双氧水、次氯酸钠或高氯酸中的一种或几种按任意比例组合。
6.根据权利要求1所述的制备方法,其特征在于所述的钯盐选自氯化钯或醋酸钯。
7.根据权利要求1所述的制备方法,其特征在于所述的超声波喷涂吸附技术,吸附液用量等于活性炭的饱和吸附量的40%-90%。
8.根据权利要求1所述的制备方法,其特征在于所述的碱选自碱式碳酸盐、碳酸氢盐或碱土金属氧化物中的一种或几种按任意比例组合。
9.根据权利要求1所述的制备方法,其特征在于所述的还原剂选自甲醛、水合肼、硼氢化钠、氢气或甲酸钠中的一种。
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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