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基于催速失活的柴油中芳烃加氢失活动力学模型

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石油学报（石油加工） 2024年第2期40卷 472-479页

作者：章晓岩丁石胡志海聂红中石化石油化工科学研究院有限公司北京100083

采用中型固定床加氢实验装置,以混合柴油为原料,对柴油加氢催化剂采用催速失活的方法进行处理,研究比较不同活性的柴油加氢NiMo催化剂的芳烃加氢饱和反应规律。结果表明,通过催速失活方法得到的催化剂相比新鲜剂发生了明显的失活,催化... 详细信息

采用中型固定床加氢实验装置,以混合柴油为原料,对柴油加氢催化剂采用催速失活的方法进行处理,研究比较不同活性的柴油加氢NiMo催化剂的芳烃加氢饱和反应规律。结果表明,通过催速失活方法得到的催化剂相比新鲜剂发生了明显的失活,催化剂的活性损失随着反应时间增加、氢/油体积比减少而增加。在考虑催化剂活性损失的基础上建立三集总多环芳烃加氢饱和失活动力学模型,将计算得到的催速失活实验中活性系数与反应时间和氢/油体积比相关联,得到柴油加氢芳烃饱和活性系数模型,并通过失活动力学模型计算不同活性系数下多环芳烃含量的变化规律。

关键词：芳烃加氢饱和失活动力学柴油活性系数

Medium-Pressure Hydro-upgrading (MhuG) Technology for Producing Clean Diesel Fuel

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China Petroleum Processing & Petrochemical Technology 2012年第1期14卷 1-7页

作者： Jiang Donghong Zhang Yuying hu zhihai Nie Hong Research Institute of Petroleum Processing Beijing 100083

This article introduces the development and application of the medium-pressure hydro-upgrading(MhuG) technology developed by the Research Institute of Petroleum Processing(RIPP).The MhuG technology based on the chemistry of diesel hydro-upgrading reactions has the advantages of flexible product slate and excellent product quality that can increase the cetane rating of diesel fuel up to more than 15 units.The hydrotreating and hydro-upgrading catalysts associated with the MhuG technology have outstanding performance to meet the demand of MhuG technology for hydro-saturation and selective ring-opening of aromatic rings.New MhuG process flow scheme can further increase the yield and selectivity of target products.Commercial application of multiple MhuG units has revealed that the MhuG technology designated for clean diesel production features good feedstock adaptability and operating stability.

关键词：加氢改质装置高科技技术清洁柴油水电生产中压商业化应用改质技术

Effectiveness of herb-partitioned moxibustion combined with electroacupuncture on polycystic ovary syndrome in patients with symptom pattern of kidney deficiency and phlegm-dampness

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Journal of Traditional Chinese Medicine 2021年第6期41卷 985-993页

作者： ZHAO Qingyi SUN Yi ZHOU Jing GAO Yanling MA Guizhi hu zhihai WANG Yi SHI Yin Graduate School Shanghai University of Traditional Chinese MedicineShanghai 201203China Department of Acupuncture and Moxibustion Shanghai TCM-Integrated HospitalShanghai University of Traditional Chinese MedicineShanghai 200082China Key Laboratory of Acupuncture and Immunological Effects Yueyang Hospital of Integrated Traditional Chinese and Western Medicine Affiliated to Shanghai University of Traditional Chinese MedicineShanghai 200437China Outpatient Department Shanghai Research Institute of Acupuncture and MeridianShanghai 200030China

OBJECTIVE:To observe the effect of herb-partitioned moxibustion combined with electroacupuncture on polycystic ovary syndrome(PCOS)in patients with symptom pattern of kidney deficiency and phlegm-dampness.METHODS:Totally 62 PCOS patients who met the inclusion criteria were randomly divided into intervention group and control group.In the intervention group,acupoints were subjected to(43±1)℃herb-partitioned moxibustion and electroacupuncture treatment.In the control group,acupoints were subjected to(37±1)℃herb-partitioned moxibustion and sham electroacupuncture treatment.Treatment was provided 3 times per week for 12 weeks,and the treatment was stopped during menstruation.After the treatment,the clinical efficacy,the Traditional Chinese Medicine(TCM)symptom pattern score,basal body temperature(BBT)levels,menstrual cycle,and related sex hormone levels of the two groups were evaluated.RESULTS:Sixty patients were eventually included in the study(30 in the intervention group and 30 in the control group).There were not obvious between-group differences in the baseline efficacy parameters(all P>0.05).(a)After treatment,the two groups have improved in terms of clinical efficacy,TCM symptom pattern score,menstrual cycle and,BBT(P<0.01,<0.05),and the intervention group was better than the control group(P<0.01,<0.05).(b)In the intervention group,the estradiol(E2)and P450 aromatase(P450 arom)levels were increased(all P<0.05),the testosterone(T)level was decreased(P<0.05),and the luteotropic hormone(LH)and anti-Müllerian hormone(AMH)levels were significantly decreased(P<0.01).In the control group,E2 level was increased(P<0.05),and LH level was decreased(P<0.05).After treatment,the T,LH,and AMH levels of the intervention group were decreased compared with those of the control group(all P<0.05),and the P450 arom level was increased(P<0.05).CONCLUSIONS:Herb-partitioned moxibustion combined with electroacupuncture can effectively improve the related clinical symptoms of PCOS patients with kidney deficiency and phlegm-dampness.Her

关键词： moxibustion patients pattern

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分子筛类型对丁基苯加氢裂化反应的影响

石油学报（石油加工） 2024年第3期40卷 660-669页

作者：高薇雅胡志海杨平任亮严张艳中石化石油化工科学研究院有限公司北京100083

以丁基苯为模型化合物,分别采用HY、Beta、ZSM-5、MOR分子筛为酸性组分制备4种NiMo/(Al_(2)O_(3)+分子筛)催化剂,采用高压加氢微型反应装置进行加氢裂化反应实验,系统考察分子筛类型对丁基苯转化率及脱烷基/断侧链、环化、脱氢等产物分... 详细信息

以丁基苯为模型化合物,分别采用HY、Beta、ZSM-5、MOR分子筛为酸性组分制备4种NiMo/(Al_(2)O_(3)+分子筛)催化剂,采用高压加氢微型反应装置进行加氢裂化反应实验,系统考察分子筛类型对丁基苯转化率及脱烷基/断侧链、环化、脱氢等产物分布的影响。结果表明:在温度340~400℃、压力4.0 MPa、氢气/丁基苯体积比500、反应时间2 h的条件下,丁基苯主要发生脱烷基/断侧链反应和环化反应;4种催化剂上,提高反应温度均有利于丁基苯的转化和脱烷基/断侧链反应的发生,同时抑制了环化与环化脱氢反应。当丁基苯转化率相近(约46%)时,分子筛类型对产物尤其是苯、甲苯、乙苯、二甲苯等轻质芳烃混合物(BTEX)的收率与分布影响显著,具有十二元环结构的分子筛催化剂NiMo/(Al_(2)O_(3)+HY)、NiMo/(Al_(2)O_(3)+Beta)、NiMo/(Al_(2)O_(3)+MOR)上BTEX选择性较高,分别为40.41%、37.04%、43.65%;而十元环结构分子筛催化剂NiMo/(Al_(2)O_(3)+ZSM-5)上BTEX选择性仅有19.30%。分子筛上总酸量也是影响BTEX选择性的重要因素,总酸量最低的NiMo/(Al_(2)O_(3)+MOR)催化剂上BTEX选择性较高。

关键词：丁基苯加氢裂化 HY分子筛 ZSM-5分子筛轻质芳烃环化脱氢

铟基催化剂混合晶型调控对CO_(2)加氢制甲醇反应的影响

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石油学报（石油加工） 2024年第4期40卷 983-992页

作者：王宇李红伟吴玉胡志海中石化石油化工科学研究院有限公司北京100083

CO_(2)是主要的温室气体,其化工转化近年来成为研究热点。对于CO_(2)加氢制甲醇反应,六方晶型结构铟基催化剂(h-In 2O_(3))具有低CO_(2)转化率和高甲醇选择性,立方晶型结构铟基催化剂(c-In 2O_(3))具有高CO_(2)转化率和低甲醇选择性。... 详细信息

CO_(2)是主要的温室气体,其化工转化近年来成为研究热点。对于CO_(2)加氢制甲醇反应,六方晶型结构铟基催化剂(h-In 2O_(3))具有低CO_(2)转化率和高甲醇选择性,立方晶型结构铟基催化剂(c-In 2O_(3))具有高CO_(2)转化率和低甲醇选择性。为保持六方晶型铟基催化剂的高甲醇选择性且提高其CO_(2)转化率,采用水热法通过控制水热时间,在六方晶型结构的铟基催化剂上添加立方晶型结构,制备得到分别含质量分数33%和62%立方晶型结构的催化剂样品In-33c和In-62c,并评价其催化剂性能。采用XRD、XPS、H 2-TPR、CO_(2)-TPD、N 2物理吸附-脱附等分析方法对所制备的催化剂进行表征。结果表明:与h-In 2O_(3)相比,In-33c和In-62c样品的催化效果均有提升,2种晶型具有协同作用,且In-62c的催化效果优于In-33c;在反应温度300℃、反应压力3.0 MPa条件下,In-62c催化剂的CO_(2)转化率达到10.8%、甲醇选择性达到80.4%;与h-In 2O_(3)催化剂相比,CO_(2)转化率相对提高了63.4%,甲醇选择性相对提高了22.2%。

关键词：氧化铟晶型立方晶型六方晶型二氧化碳加氢甲醇

Development and Application of Hydrocracking Catalysts RHC-1/RHC-5 for Maximizing High Quality Chemical Raw Materials Yield

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China Petroleum Processing & Petrochemical Technology 2018年第2期20卷 41-47页

作者： Mao Yichao Nie Hong Li Mingfeng hu zhihai Zhao Guangle Zhao Yang SINOPEC Research Institute of Petroleum Processing Beijing 100083

To adapt to the change in the demand of the oil refining market,two hydrocracking catalysts,RHC-1 and RHC-5,were developed to improve the quality of tail oil.The catalysts were designed based on the theory of selective ring-opening.By selecting more acidic molecular sieves,the problem of poor selectivity of conventional materials can be solved to properly match up to the hydrogenation performance of catalysts.Compared with the performance of previous catalysts,the quality of the tail oil achieved by the said catalysts is better,and the BMCI is reduced by 1—2 units.In the long cycle operation of the petroleum industry,the good quality of the tail oil has been verified and the adaptability of the process conditions is good.When the RHC-1 catalyst is used to process heavy feed under medium pressure,a BMCI value of about12 can be obtained along with a nearly 60%yield of tail oil.The total yield of chemical raw material(steaming cracking feed+catalytic reforming feed)can exceed 80%,and the hydrogen consumption has dropped by nearly 50%as compared to the conventional hydrocracking conversion rate.When processing a mixed CGO and VGO feed with the full conversion mode under a hydrogen pressure of 13.0 MPa,the RHC-5 catalyst can yield about 68.4%of heavy naphtha with a potential aromatic content of up to 50.6,while the total yield of chemical raw materials can reach more than 98%.The results of industrial application of these catalysts show that more than 30%of high quality tail oil can be obtained via processing of inferior quality feed,and its BMCI value can reach 10.7.The total yield of chemical raw materials can reach more than65%.The industrial operation process has implemented two operating cycles totaling 8 years.

关键词：裂解催化剂化学原料质量氢化开发最大化周期操作石油工业

Herb-partitioned moxibustion regulated the miRNA expression profile in the thyroid tissues of rats with experimental autoimmune thyroiditis

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Journal of Traditional Chinese Medicine 2021年第5期41卷 789-798页

作者： WANG Zhaoqin CUI Yunhua huANG Yan WU huangan ZHAO Jimeng HE Jinsen LIU huirong ZHENG Handan WU Luyi hu zhihai LIU Yanan Department of Aeronautics and Astronautics Shanghai Key Laboratory of Acupuncture Mechanism and Acupoint FunctionFudan UniversityShanghai 200433China Key Laboratory of Acupuncture and Immunological Effects Shanghai University of Traditional Chinese MedicineShanghai 200030China Yueyang Hospital of Integrative Chinese and Western Medicine Shanghai University of Traditional Chinese MedicineShanghai 200437China Shanghai TCM-integrated Hospital Shanghai University of Traditional Chinese MedicineShanghai 200082China

OBJECTIVE:To observe the effect of herb-partitioned moxibustion(HPM)on the miRNA expression profile of thyroid tissue in experimental autoimmune thyroiditis(EAT)rats.METHODS:Rats were randomly divided into normal control(NC)group,EAT model(EAT)group,HPM group and western medicine(Med)group.EAT model rats were prepared by a combined immunization with complete and incomplete Freund’s adjuvant emulsified with porcine thyroglobulin and iodine.Rats in the HPM group were treated with HPM,while rats in the Med group were treated with levothyrocine(1μg/2 m L)by gavage.HE staining was used to observe the pathological morphological changes of thyroid tissue,ELISAs was uaed to detect the serum concentrations of TGAb,TPOAb,FT3,FT4,TSH.We then performed high-throughput mi RNA sequencing to analyse the mi RNA expression profiles in the thyroid tissues,followed by a bioinformatics analysis.RT-q PCR was used to verify the identified differentially expressed mi RNAs.RESULTS:HPM improved the thyroid tissue morphology and reduced serum TPOAb,TGAb,TSH concentration in EAT rats(P<0.05),but with no obvious effect on FT3 and FT4 concentration.While the TSH,FT3 and FT4 concentration was significantly changed in the Med group(P<0.01 or P<0.05)compared with that of EAT group.Sequencing results showed that a total of 17 mi RNAs were upregulated,and 4 were downregulated in the EAT rats,in which the expression levels of mi R-346 and mi R-331-5 p were reversed by HPM.The target genes of the mi RNAs that regulated by HPM wereassociated with a variety of immune factors and immune signals.RT-q PCR verification showed that the expression of mi RNA-346 and mi RNA-331-5 p was consistent with the sequencing results.CONCLUSIONS:HPM could regulate the the expression of mi RNA-346 and mi RNA-331-5 p,then act on their target genes to immune and inflammation-related pathways,which may be one of the mechanisms of HPM on EAT rats.

关键词： Experimental autoimmune thyroiditis Herb-partitioned moxibustion miRNA expression profile Immuneregulation

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加氢裂化催化剂RHC-133的开发与应用

石油炼制与化工 2024年第3期55卷 1-8页

作者：董松涛赵阳赵广乐胡志海莫昌艺中石化石油化工科学研究院有限公司北京100083

中石化石油化工科学研究院有限公司开发了新一代加氢裂化催化剂RHC-133,该催化剂与第三代尾油型加氢裂化催化剂相比,喷气燃料选择性更高,尾油质量更优。RHC-133催化剂在中国石化齐鲁分公司的工业应用结果表明:使用该催化剂,高压加氢裂... 详细信息

中石化石油化工科学研究院有限公司开发了新一代加氢裂化催化剂RHC-133,该催化剂与第三代尾油型加氢裂化催化剂相比,喷气燃料选择性更高,尾油质量更优。RHC-133催化剂在中国石化齐鲁分公司的工业应用结果表明:使用该催化剂,高压加氢裂化装置的喷气燃料收率较上一周期提高3.75百分点,质量可满足3号喷气燃料的主要指标要求;柴油十六烷指数达到58.9,凝点为-47℃,可作为低凝柴油;尾油BMCI较上一周期降低2.0,低至9.7,是优质的蒸汽裂解制乙烯原料,装置取得了显著的经济效益和社会效益。RHC-133催化剂在中国石油某炼油厂的应用也同样取得了近似的良好效果。

关键词：加氢裂化喷气燃料尾油 BMCI

LCO高效加氢转化关键技术专用催化剂的开发与应用

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石油炼制与化工 2024年第4期55卷 1-7页

作者：杨平李明丰任亮胡志海聂红刘诗哲中石化石油化工科学研究院有限公司北京100083

面向解决催化裂化轻循环油(LCO)出路和富余柴油产能高值化利用的重大需求,以破解LCO加氢转化过程中芳环的加氢、环烷环的开环、烷基侧链的裂化和聚合结焦等关键反应对催化剂活性中心需求不一致的矛盾为切入点,通过创制新型催化材料、优... 详细信息

面向解决催化裂化轻循环油(LCO)出路和富余柴油产能高值化利用的重大需求,以破解LCO加氢转化过程中芳环的加氢、环烷环的开环、烷基侧链的裂化和聚合结焦等关键反应对催化剂活性中心需求不一致的矛盾为切入点,通过创制新型催化材料、优化金属体系并改善制备方法等措施,开发了定向强化开环反应的柴油加氢改质催化剂RIC-3和兼具高开环与高断侧链性能的柴油加氢裂化专用催化剂RHC-100,构建了提高催化剂活性中心有效性、定向性和高效性的活性中心精细调控关键技术平台,形成了以RIC-3和RHC-100为核心、靶向调控多环芳烃加氢开环与裂化反应活性与选择性的催化剂族,可将劣质LCO转化为清洁柴油组分或高辛烷值汽油调合组分,为多环芳烃高效加氢转化技术的开发与应用提供技术支撑。

关键词：催化裂化轻循环油加氢改质加氢裂化四氢萘开环反应断侧链