02 第二章 绿色化学.ppt

第1页：第二章 绿色化学

Chapter 2 Green Chemistry

第2页：第二章 章节导航

• 2.1 The concept of Green Chemistry
• 2.2 Promoting the development of Green Chemistry
• 2.3 Atom Economy of chemistry reaction
• 2.4 Atom Economy and environmental effects
• 2.5 Research area of green chemistry
• 2.6 Twelve principles of green chemistry References

第3页：2.1 绿色化学的概念

2.1 The concept of Green Chemistry Green Chemistry is investigated world-widely

第4页：绿色化学的重要性

第5页：野依良治论绿色化学

Noyori: Importance of Green Chemistry Without Green Chemistry, chemical manufacturing will be unable to survive into the 22 nd century.

第6页：绿色化学的内涵

Green Chemistry The connotation of Green Chemistry A deeper view of

第7页：绿色化学的内涵（一）

The connotation(内涵) of Green ChemistryGreen chemistry is an active inter crossing(交叉) research area in the world, it deals with the frontier of chemical research.The traditional ways of environmenta

第8页：原则的适用范围

The connotation of Green ChemistryGreen Chemistry provides ways to reduce or eliminate(消除) environmental pollution from the beginning, which could have eternal(永远的)benefits.

• The principles of Green Chemistry could and should be used to all domain(领域) of chemistry and chemical engineering.

第9页：源头消除污染

The connotation of Green ChemistryNo pollution should be accompanied in chemical processes, this is to say,eliminate the potential(潜力) of pollution before it occurs.The realization of this goal mean

第10页：绿色化学的内涵（二）

The connotation of Green Chemistry

• Green Chemistry is the utilization of a set of principles to reduce or eliminate the use of hazardous(危险的) materials in the design, manufacture and use of chemicals,
• and these chemicals themselves should be economically and environmentally benign(仁慈的).
• It deals also with the reduction and elimination of the use of hazardous materials in the design and use of chemical processes. Green Chemistry

第11页：绿色化学的内涵（三）

The connotation of Green Chemistry

• Green Chemistry is the application of chemical principles, chemical technologies and chemical methods to all chemicals and chemical processes to reduce or eliminate the use of hazardous starting materials,hazardous processes,hazardous target products,hazardous auxiliary substances(such as solvents, separation agents) in the production and use of chemicals. Green Chemistry

第12页：减少有害过程

The connotation of Green Chemistry

• Hazardous or potentially hazardous processes should also be reduced or eliminated.
• By-products are expected to be avoided as thoroughly as possible
• and the starting materials be utilized as completely as possible
• thus satisfying a sustainable civilization. Green Chemistry

第13页：绿色化学的内涵（四）

The connotation of Green Chemistry

• Green chemistry is the science which uses chemical principles and methods to reduce or eliminate the use of hazardous starting materials, catalysts, solvents, reaction agents, target products, by-products, etc., which are toxic(有毒的) or harmful to human beings and environment.
• It is the chemistry which could reduce and eliminate pollution from the very beginning and cure pollution eternally.

第14页：绿色化学的解决方案

Environment &resource Simultaneously give out Green Chemistry Solution Recyclable economy Sustainable development Crises Requirement Green Chemistry

第15页：内涵与深层认识导航

Green Chemistry The connotation of Green Chemistry A deeper view of

第16页：绿色化学可以实现

Green Chemistry is realizable

• The goal of green chemistry is to seek for perfection (by overcoming difficulties).
• Synthesis efficiency is highly thought of in green chemistry.
• Opposite opinions:it is difficult to quantify the toxicity(毒性) and harmfulness(危害) of a substance to human beings and to environment.

第17页：方案比较与选择

• We could compare and select the most favorable substance and method under specified conditions. Green Chemistry is realizable
• Examples already realized give evidences to illustrate strongly that green chemistry is realizable.
• Relationship between structure and properties ——gives us clue to predict the harmfulness of substances.

第18页：治标与治本之别

Green chemistry way Bring about a temporary solution Treat the existed waste Treat waste Provide a permanent cure Eliminate waste from the origin No waste produced Not need for waste treatment Traditi

第19页：绿色化学的深层认识

Green Chemistry The connotation of Green Chemistry A deeper view of

第20页：科学发展观的体现

Deeper View

• Green Chemistry is one of the concrete embodiment(体现) of the Viewpoint of Scientific Development(科学发展观).
• Green Chemistry provides basic scientific principles and technologies to support the Viewpoint of Scientific Development and Recyclable Economy(循环经济).

第21页：科学层面的认识

Deeper viewpoints on Green ChemistryScientific viewpoints:

• Green Chemistry concerns new research area of chemistry. It rejuvenates(更新) the contents of chemistry. Environmentally benign Starting materials Target products High selectivity, atom economy(原子经济性)

第22页：经济层面的认识

Economical viewpoint:

• Green Chemistry provides fundamental principles and techniques to utilize effectively the starting materials(resources) and energy
• meanwhile the cost of the production is reduced
• thus satisfying the requirements of sustainable development. Deeper viewpoints on Green Chemistry

第23页：环境层面的认识

Environmental viewpoint:

• Green Chemistry provides new principles and techniques to cut down pollution originally(从源头上) and eternally. Deeper viewpoints on Green Chemistry

第24页：第二章 章节导航

• 2.1 The concept of Green Chemistry
• 2.2 Promoting the development of Green Chemistry
• 2.3 Atom Economy of chemistry reaction
• 2.4 Atom Economy and environmental effects
• 2.5 Research area of green chemistry
• 2.6 Twelve principles of green chemistry References

第25页：2.2 推动绿色化学发展

Why 2.2 Promoting the development of Green Chemistry

第26页：可持续发展的需要

Satisfying the demand for sustainable development of human society

第27页：传统化工的伴生危害

Strongly develop green chemistry to satisfy the demand for sustainable development of human society Traditional chemical Industry is accompanied by unexpected harm (3 aspects) No other alternatives ex

第28页：环境与资源的双重需求

Environment &resource Simultaneously give out Green Chemistry Solution Recyclable economy Sustainable development Crises Requirement Green Chemistry

第29页：科学与经济发展的要求

Satisfying the requirement for the development of science and economy Chemistry itself develops in accordance with the change of resources and of the social requirement. It should also be renewed in methodology and content. Green chemistry appears.

• Scientifically:

第30页：化工产业的地位

• Chemical industry plays an important role inthe industrial ensemble Britain, Germany, USA
• Chemical enterprises make great effects to reduce their cost, and increase their cost by treating the pollutants they produced.
• Green chemistry provides new ways which could satisfy both the demands of chemical production. Satisfying the requirement for the

第31页：第二章 章节导航

• 2.1 The concept of Green Chemistry
• 2.2 Promoting the development of Green Chemistry
• 2.3 Atom Economy of chemistry reaction
• 2.4 Atom Economy and environmental effects
• 2.5 Research area of green chemistry
• 2.6 Twelve principles of green chemistry References

第32页：2.3 化学反应的原子经济性

2.3 Atom Economy of Chemical Reaction(化学反应的原子经济性)

第33页：原子利用率与原子经济

Atom utilization Atom economy of chemical reaction Increase the conversion of the reactants, the selectivity of the products

第34页：原子利用率的提出

2.3.1. Atom utilization(原子利用率) The concept was used to quantify the waste (by-products) formed when a certain amount of target product was manufactured in a chemical reaction. Roger A. Sheldon 1992

第35页：谢尔登（R. A. Sheldon）

R. A. Sheldon, 2005.5 Zhu hai

第36页：原子利用率计算式

Atom utilization==The amount of target product formed╳100%The amount of all products formed stoic hio metrically The amount of reactants used The amount of target product formed╳100%Atom utilization

第37页：完全原子利用的特征

The two main characteristics of chemical reaction with 100% atom utilization:

• The reactants could be fully utilized, and the resource could be most possibly used economically
• The waste could be minimized 原子利用率=目标产物的量按化学计量式所得所有产物的量之和=目标产物的量各反应物的量之和╳100%╳100%

第38页：三个计算示例

Examples Example 1 ：The preparation of epoxy-ethane(环氧乙烷) from ethylene more Example 2：The preparation of epoxy-propane(环氧丙烷) more Example 3：The synthesis of methyl a cry late(丙烯酸甲酯)more

第39页：例1 环氧乙烷的制备

Example 1 The preparation of epoxy-ethane

第40页：传统氯醇法反应式

Traditional way CH 2=CH 2+ Cl 2+ H 2 Oas hs ska Cl CH 2 CH 2 OH + H Clash s ska Cl CH 2 CH 2 OH + Ca(OH)2+ HCl C 2 H 4 O + Ca Cl 2+ 2 H 2 OCH 2=CH 2+ Cl 2+ Ca(OH)2 C 2 H 4 O + Ca Cl 2+ H 2 Oaska 28717

第41页：环氧乙烷传统法的弊端

Disadvantages of the traditional method

• 1. The atom utilization could reach only 25%,i.e., 1 kg of target product / 3 kg of wastes.
• 2. The reactant Cl 2 is harmful, it erodes(腐蚀)the equipment and injures(伤害) human beings, thus demanding special equipment and special protection measure.
• 3. Separation and purification(纯化) processes are necessary to obtain useful product. If every step could obtain 100% selectivity and 100% yield, then

第42页：银催化直接氧化法

Silver catalyst is used to convert ethylene directly to the target molecule by using oxygen as the oxidant, which gives 100% atom utilization. New greener way CH 2=CH 2+ 1/2 O 2 ash s ska 44 C 2 H 4 O

第43页：环氧乙烷新法的优势

High atom economy(100%)Oxygen is safe to human beings andto environment.No separation or purification is needed. Advantages of the new greener method If the selectivity of the reaction could reach

第44页：例2 环氧丙烷的制备

Example 2 The preparation of epoxy-propane

第45页：传统法原子利用率计算

ka 4271587411118 ash s ska asha asha asha 58 asha 111+ 18 = 12958111+ 18 + 58╳100%=5842+ 71 + 74╳100%=31%C 3 H 6 O + Ca Cl 2+ H 2 OCH 3 CH=CH 2+ Cl 2+ Ca(OH)2=Traditional way

第46页：环氧丙烷传统法弊端

Disadvantages of the traditional method

• 1. The atom utilization could reach only 31%,i.e., 1 kg of target product / 2 kg of wastes.
• 2. The reactant Cl 2 is harmful, it erodes the equipment and injures human beings, thus demanding special equipment and special protection measure.
• 3. Separation and purification processes are necessary to obtain useful product. If every step could obtain 100% selectivity and 100% yield, then

第47页：钛硅分子筛催化氧化

Direct oxidation catalyzed by titania-silica New greener wayka 42345818 ash s ska as haas ha C 3 H 6 O + H 2 OCH 3 CH=CH 2+ H 2 O 2 Ashs ska Titania-s illica molecular sieve ash s ska 5818 asha 5858 +

第48页：环氧丙烷新法的优势

The atom utilization is high(76 %)The by-product----water is environmentally benign.Hydrogen peroxide is safer than chlorine to human beings and to environment. Advantages of the new greener method

第49页：直接氧化的问题

Problem?CH 3 CH=CH 2+ 1/2 O 2 C 3 H 6 O

第50页：例3 丙烯酸甲酯的制备

Example 3 The preparation of methyl a cry late(丙烯酸甲酯)

第51页：丙酮氰醇路线

This process uses the by-products from phenol (苯酚) industry and acrylonitrile (丙烯腈):acetone and hydro cyan ic acid H 3 CCOCH 3 HCN Traditional way

第52页：丙酮氰醇法反应式

Traditional way held CH 3 C(CN)(OH) CH 3 CH 3 COCH 3+ HCN Ahs ska CH 3 OOC(CH 3) C=CH 2 + NH 4 HSO 4 CH 3 OH, H 2 SO 4 CH 3 COCH 3+ HCN + CH 3 OH + H 2 SO 4 CH 3 OOC(CH 3) C=CH 2 + NH 4 HSO 4 AA 100+1

第53页：丙烯酸甲酯传统法弊端

Disadvantages of the traditional method

• 1. The atom utilization could reach only 46%,i.e., 1 kg of target product / 1 kg of wastes.
• 2. The reactant HCN is harmful, it erodes the equipment and injures human beings, thus demanding special equipment and special protection measure.
• 3. Separation and purification processes are necessary to obtain useful product. If every step could obtain 100% selectivity and 100% yield, then

第54页：丙炔与一氧化碳路线

This process utilizes the by-product pro pyne CH 3 C≡CH from the dissociation (e.g. Pyrolysis(热解)) of naphtha(石脑油), and carbon monoxide. New greener way

第55页：醋酸钯催化新法

Using palladium acetate Pd(OAc)2 as the catalyst，developed in 90’s New greener way Pd(OAc)2

第56页：丙烯酸甲酯新法优势

The atom utilization is high(100 %)Carbon monoxide and methanolaresaferthanhydrocyanic acid to human beings and to environment.No waste produced Advantages of the new greener method If the selectiv

第57页：原子经济反应的定义

2.3.2 Atom economy of chemical reaction Definition：The ratio of atoms appeared in the target molecules to all the atoms of the reactants The reaction with 100% atom utilization is ideal atom economica

第58页：如何设计原子经济反应

How to design atom economical reactions?如何设计原子经济反应

第59页：传统合成方式的缺陷

Deficiency of the traditional synthetic ways A + BC ＋D waste Target molecule

第60页：副产物不可避免

For a target molecule CIf the traditional way is A + BC +DThis process inevitably produces theby-product D, which should be treated and could be considered as waste. Because this is the chemical react

第61页：原子经济反应模式

Atomic economic reactions E + FC Target product

第62页：原子经济反应的优点

Thus we should design new atom economical reactions as E + FC Advantages: all the atoms in the reactants E and F entered in the target molecule C, making the atom utilization be 100%. No by-product fo

第63页：课堂提问

Problem

• The types of organic reactions: Please answer
• Which kinds are atomic ally economical?

第64页：例：卤代烃的合成

Example The synthesis of halo alkane 卤代烃

第65页：加成与取代的对比

Atom economy: 100%No by-product No pollution The consumption of resource is minimized。

3 moles target molecules/1 mole by-product, Waste resources and the by-product is a kind of pollutant 3 ROH + PX 33 RX + H 3 PO 4 RX’ + Na X RX + Na X’R’CH=CH 2 + HXRX 1 mole target molecules/1 mole by-product，Waste resources and the by-product is a kind of pollutant

第66页：提高资源利用效率

Use the natural resource more efficiently, prolong their lifetime. Study on atomic economic reactions Chiral technique All atoms from reactants enter into the target molecule All atoms from reactants

第67页：转化率与选择性

2.3.3 Increase the conversion of the reactants and the selectivity of the products as thoroughly as possible Atom economy is necessary for a reaction to not produce waste, but it is not enough. Low eq

第68页：第二章 章节导航

• 2.1 The concept of Green Chemistry
• 2.2 Promoting the development of Green Chemistry
• 2.3 Atom Economy of chemistry reaction
• 2.4 Atom Economy and environmental effects
• 2.5 Research area of green chemistry
• 2.6 Twelve principles of green chemistry References

第69页：2.4 原子经济与环境效应

2.4. Atom Economy and environmental effects

第70页：环境因子的定义

2.4.1. Environmental factor It is used to quantify the effects of production process to the environment Idea: All other compounds formed other than the target product are considered to be WASTE. Roger

第71页：环境因子计算式

Environmental factor E=The amount of waste The amount of target product The larger EThe more waste formed The more serious the pollution If the atom Utilization=100%E=0

第72页：各行业的环境因子

第73页：环境商的引入

But the environmental pollution is strongly associated with the harmful performance of the waste.2.4.2. Environmental quotient(EQ) The E factor just gives the ratio of the waste and the target product

第74页：环境商计算式

Environmental quotient E-----Environmental factor Q-----The extent of hazardous ness of the waste to the environment obtained from the performance of the waste in the environment. EQ＝E×Q

第75页：第二章 章节复页

Chapter 2 Green Chemistry

第76页：第二章 章节导航

• 2.1 The concept of Green Chemistry
• 2.2 Promoting the development of Green Chemistry
• 2.3 Atom Economy of chemistry reaction
• 2.4 Atom Economy and environmental effects
• 2.5 Research areas of green chemistry
• 2.6 Twelve principles of green chemistry References

第77页：2.5 绿色化学的研究领域

2.5 Research areas of green chemistry

第78页：五个研究方向

Designing safer and effective target molecules Seeking for safer starting materials Seeking for safer synthetic processes Seeking for new safer conversion ways Seeking for safer new reaction condition

第79页：2.5.1 设计安全有效的分子

2.5.1. Designing safer and effective target molecules The target molecule being safe is prior toall considerations, and it should also be effective.

第80页：构效关系与分子操作

The designing of safer chemicals is the useof the relationship between molecular structure and properties(structure-activity relationship, SAR)and molecular manipulation(操作) method to obtain molecules

第81页：目标分子设计的两方面

• 1. The designing of new safe and effective molecules.
• 2. The designing of new safer and effective molecules to replace the molecules which existed effective but not benign

第82页：化合物数量的增长

We have more than 18,000 thousands of compounds up to now, while 600 thousands of new compounds appear every year. Designing safer and effective target molecules

第83页：传统与新设计方式

Designing safer and effective target molecules Traditional ways of finding an effective molecule: Practical needssynthesistestsynthesistest New molecular designing ways : Trial and errors Practical ne

第84页：实验台与计算机

Working desk+computer+ventilation cupboard Designing safer and effective target molecules

第85页：2.5.2 寻找新起始原料

2.5.2. Seeking for New starting materials

第86页：替代有毒有害原料

Seeking new starting materials to substitute the actually used hazardous and poisonous materials Example 1 Using CO 2 to substitute phosgene（光气）in the synthesis of polyurethane(聚氨酯) Example 2 Eliminat

第87页：消除光气的使用

Eliminating the poisonous phosgene in the synthesis of polyurethane and polycarbonate Example 1

第88页：光气的工业用途

Polycarbonate(聚碳酸酯) Phosgene is widely used for the production of:isocyanate (异氰酸酯)polyurethane(聚氨酯)

第89页：传统异氰酸酯合成

Isocyanate is first synthesized by the reaction of phosgene and amine, and then using isocyanate to produce polyurethane. Traditional way 按照化学 RNH 2 + COCl 2 RNCO + 2 HCl R NHC O 2 R 1 The synthesis o

第90页：光气的官能团作用

What kinds of functional group would phosgene provide in a chemical reaction?Which kind of compound could be employed to substitute phosgene?providing -CO group

第91页：二氧化碳替代光气

Carbon dioxide is used to substitute phosgene in the production of isocyanate (providing carbonyl group) The function of phosgene: providing -CO group 按照化学 RNH 2 + CO 2 RNCO + H 2 OR NHC O 2 R 1 New g

第92页：二氧化碳法反应式

按照化学 The synthesis of isocyanate using CO 2 C 6 H 5 NH 2+ CO 2 C 6 H 5 N(H) CO 2 HC 6 H 5 N=C=O–H 2 O Ani line

第93页：碳酸二甲酯的合成对比

按照化学 2 CH 3 OH + COCl 2 CH 3 OO CO OCH 3+ 2 HCl 2 CH 3 OH + CO + ½O 2 CH 3 OO CO OCH 3+ H 2 O Catalyst 2 CH 3 OH + CO 2 CH 3 OO CO OCH 3+ H 2 O Thermodynamics, Catalyst, Reaction conditions: temperatu

第94页：消除氢氰酸的使用

The elimination of the use of HCN(hydro cyan ic acid)(hydrogen cyanide,prussi c acid)by changing the process Example 2

第95页：氢氰酸的用途

Hexane di nitrile(己二腈); Series of methyl prope no ic acid(甲基丙烯酸系列); Series of intermediate chemicals such as chel at or / ch elating agent(螯合剂), methionine (蛋氨酸) etc. Hydro cyan ic acid HCNis widely u

第96页：亚氨基二乙酸二钠传统法

The synthesis of sodium im in odi-acetate(亚氨基二乙酸二钠) Traditional way involves two steps:按照化学 NH 3 + 2 CH 2 O + 2 HCN—①NCCH 2 NHCH 2 CN—②+ 2 Na OH → Na O 2 CCH 2 NHCH 2 CO 2 Na + NH 3

第97页：二乙醇胺替代路线

A new starting material HOCH 2 CH 2 NHCH 2 CH 2 OH(di ethanol amine, 二乙醇胺) is used New greener way

第98页：己二酸与己二胺的合成

Replacing HCN The synthesis of adi pic acid ( /hexane di oic acid 己二酸) and hex a methylene dia mine (己二胺) CH 2=CHCH=CH 2+ HCN NC CH 2 CH 2 CH 2 CH 2 CN HOO C(CH 2)4 COOHH 2 N(CH 2)6 NH 2 Traditional m

第99页：环己烷氧化路线

Replacing HCNC 6 H 12 The oxidation of Cyclo-hexane(环己烷) Oxidation HOO C(CH 2) COOH The hydro carbonyl ation of butadiene 氢甲酰化丁二烯 CH 2=CHCH=CH 2+ 2 CO + 2 H 2 OHC(CH 2)4 CHOHN=CH(CH 2)4 CH=NHH 2 N(CH

第100页：苯乙酸的合成对比

Replacing HCN The synthesis of phenyl acetic acid 苯乙酸 C 6 H 5 CH 2 Cl +HCNC 6 H 5 CH 2 CN + HCl C 6 H 5 CH 2 COOHH 2 OC 6 H 5 CH 2 Cl + COC 6 H 5 CH 2 COOH OH–/ H 2 O Traditional way New greener way

第101页：苯乙酸绿色路线之问

Can we design another green way to synthesize phenyl acetic acid with ethyl benzene and oxygen as reactant?C 6 H 5 CH 2 CH 3+ O 2 C 6 H 5 CH 2 COOH If can’t, why?

第102页：例3 己二酸的合成

Example 3 The synthesis of adi pic acid by changing starting material

第103页：传统法的弊端之问

Traditional way Could anyone tell me the disadvantages of this method

第104页：传统法的弊端

• Photochemical smog
• Depletion of ozone,
• Acid rain Disadvantages of the traditional method The starting material (Benzene)is hazardous (carcinogen tic) The release of nitrogen oxides which are multi functional pollutants Use of heavy metals (cobalt)

第105页：过氧化氢新法

Elimination of the use of solvent, the use of hazardous benzene, the corrosive capacity of hydrogen peroxide is not as severe as nitric acid,no pollutants produced. Kam zu hi ko Sato, 1998, Science, 2

第106页：葡萄糖路线

The synthesis method is widened. Drath and Frost,1990, 1991 按照化学 New greener method 2 Not only eliminate the use of benzene,but also develop a new method to use renewable biomass(glucose).

第107页：可再生原料的历史

Using of renewable starting material 150 years ago, industrial organic chemicals were all derived from biomass originated from plants

第108页：生物质的回归

The use of biomass as starting material for energy and chemicals production regain much attention, because of its renew ability. Coal Oil Natural gas Coal Starting materials Biomass Industrial revolut

第109页：能源资源的可采年限

Security and Energy Resources Oil: 30-50 years Natural Gas: 50-100 years Coal: 200-400 years

第110页：生物质的组成

It must degenerate before it could be effectively used. Biomass：Starch (淀粉, amyl um)+ Lignin (木质素, lig nine) Lignin：164 billion ts /year amount used <1.5%Using of renewable starting material

第111页：能源资源年限复页

Security and Energy Resources Oil: 30-50 years Natural Gas: 50-100 years Coal: 200-400 years

第112页：生物质原料举例

Examples Using of renewable starting material plants, trees, crops, grasses, aquatic plants and their residues or waste materials.

第113页：太阳能的主要形式

Main Feasible Forms of Solar Energy

• Hydraulic Energy: Green solar energy
• Depleting & Renewable
• Fossil Fuel: Accumulated Ancient Solar Energy Depleting
• Biomass: Renewable Animals & plants converted solar energy
• Wind
• Others

第114页：化石能源的来源

Fossil Energy Resources

• Oil
• Natural Gas
• Coal Ancient Animals and Ancient Plant Carbon fixed by ancient life-activities Ancient Solar Energy

第115页：生物质资源

Biomass Resources

• Biomass Carbon Fixed by Actual Life-activities Including Animals & Plants

第116页：农业废弃物资源量

• 5 hundreds million tons of wheat straw;
• 10 million tons of rice bran;
• 10 million tons of corncob;
• 20 million tons of rice hull;
• 7 million tons of biogas es; Using of renewable starting material about 2.8～3.5 hundreds million of tons can be used as resource of energy./year In China,

第117页：秸秆处置与资源化

第118页：秸秆焚烧的弊端

The burning of straw:：waste of resource while polluting

第119页：木质素结构与降解

• The structure of lignin and its effect on its degradation
• Orientated degradation to produce directly useful chemicals
• Handling and manipulation of oxygen-rich molecules
• The effect of impurities on the degeneration parameters and distribution of the products Using of renewable starting material Fundamental scientific challenge:

第120页：生物质利用的技术挑战

Technical challenges

• Collection of biomass
• Variation of compositions of different kinds of biomass and grown from different area of the world
• Continuous operation
• Handling of mixtures rather than pure compound
• Upgrading and Separation of the products
• How to use effectively the bio-products

第121页：生物质利用的研究进展

Using of renewable starting material Actual progresses Cross Agricultural waste (polysaccharides 多糖) Naturally de grad able polymer Sichuan University, University of Science and Technology, Shandong U

第122页：生物质的转化路径

Biomass Animal feeds Fuel Chemicals Using of renewable starting material Halt z apple from Texas A & M university 1996, The presidential Green Chemistry Award

第123页：直接液化与间接转化

Converting biomass to fuel and chemicals Direct li qu ation Biomass Liquid fuel &chemicals Indirect conversion Gasification C 3-C 4 Gases Gas fuel CO + H 2 Liquid fuel &chemicals Catalyticconversion U

第124页：固定床气化装置

Gasification reactor(fixed bed)for biomass conversiongasifierpurificationfangastank Needed By Homebiomass, air

第125页：流化床气化装置

Gasification reactor(fluidized bed)for biomass conversiongasifierairbiomasstank CO + 2 H 2=CH 3 OH methanol CO, H 2 screw feeder ash separation catalysis re ation bed reforming reaction bed biomass

第126页：流化床气化运行参数

Gasification reactor(fluidized bed)for biomass conversion Gas production：150 M 3/h Operation pressure：1 MPa Heat capacity：7 MJ/M 3 Efficiency of energy conversion：80%

第127页：速生竹与灌木资源

Fast-growing bamboo Fast-growing shrubs Convert biomass to useful products green chemically 将生物质转化为化学化工原料开发新资源实现资源持续利用 Agricultural waste

第128页：基于能源资源的化工研究

Chemical research based on energy resources Biomass Coal Oil Coal Natural Gas

第129页：化学转化关系

Chemistry Treating

• Cn H 2 n±x
• CH 4
• C Treating
• Cn H 2 n On
• C
• CO 2

第130页：生物油的提级

Crude bio-oil Upgraded bio-oil

第131页：2.5.3 设计安全合成路线

2.5.3. Seeking and designing safer and effective synthetic routes

第132页：理想合成路线

Ideal synthetic route Paul A Wender 1996 the starting material used should be the cheapest and most feasible;the operation and manipulation should be simple,safe and environmentally benign;the reactio

第133页：合成路线的重要性

• The synthetic route is a very important factor to the benign it y of a process.
• The integration of chemical reactions to make the whole process benign.
• Computer aided designing of synthetic route Designing proper synthetic route Example: The synthesis of para-phenyl ene dia mine （对苯二胺, ursol ）from nitro benzene (硝基苯, mir bane oil)

第134页：对苯二胺的合成案例

Example The synthesis of para-phenyl ene dia mine from nitro benzene Let us analyze four possible routes in a green chemistry viewpoint

第135页：路线1

Route 1

第136页：路线1 原子利用率

• The amounts of reactants:1062
• Target molecule:108
• Waste:954
• Atom utilization: The overall reaction 10%

第137页：路线2

按照化学 Route 2

第138页：路线2 原子利用率

The overall reaction

• The amounts of reactants:300
• Target molecule:108
• Waste:192
• Atom utilization:36%

第139页：路线3

按照化学 Route 3

第140页：路线3 原子利用率

The overall reaction

• The amounts of reactants:543
• Target molecule:108
• Waste:435
• Atom utilization:20%

第141页：路线4

按照化学 Route 4

第142页：路线4 原子利用率

The overall reaction

• The amounts of reactants:162
• Target molecule:108
• Waste:54
• Atom utilization:67%

第143页：四条路线的汇总分析

Ag greg at ive analysis From the viewpoint of atom economy,route 4 is the most favorable comparing to others。

In routes 1 & 2, because of the protection of-NH 2 in n it ration, one mole of acetic anhydride is needed and 2 moles of acetic acid are formed as waste, while in routes 3 & 4, the protection step was not needed.

第144页：计算机辅助设计的必要

Practical need:great amount of possible routes for a giving target molecule. Computer aided designing of synthetic route Corey and Ber so hn , 30 years ago used computer to help designing of synthetic

第145页：路线数量的爆炸

30 ⇒30×30⇒30 ×30×30⇒……⇒305 > 24 million routes It is necessary!Computer aided designing of synthetic route e. g. If the synthesis of a compound needs 5 steps, and 30 methods are possible for each step

第146页：计算技术的支撑

The progress of computation technology It is possible Computer aided designing of synthetic route The progress in computer science and technology

第147页：化学反应数据库

• Construction of a data base of chemical reactions as complete as possible.
• Put forward our requirement
• Let the computer give us the possible starting materials which could form the target molecule Technical Way Computer aided designing of synthetic route

第148页：反向搜索与路线比较

• Further search for the starting material using the former starting material as the target molecules………… until the provided starting material is needed
• Compare all possible routes, and choose the most favorable one from the viewpoint of economical and environmental effect. Technical Way Computer aided designing of synthetic route

第149页：2.5.4 寻找新转化方法

2.5.4 Seeking for new conversion methods

第150页：非常规转化方式

Catalytic plasma more Electrochemical conversion more Photo and other radiation conversion more Seeking for unconventional conversion ways

第151页：二氧化碳与甲烷制汽油

The synthesis of gasoline from carbon dioxide and natural gas(methane, 甲烷) CO 2+ CH 42 CO + 2 H 2 Gasoline→→Nickel catalyst FT process Chang jiu n Liu, Tianjin g University Traditional thinking up CO

第152页：电化学转化的作用

Using electrochemical ways

• Electricity can be used not only as an energy supply for chemical reactions, it could also affect chemical reaction in different aspects and provide new ways for it to occur.
• The following example will give us some direct information.

第153页：电化学替代有害原料

Using electrochemical ways to eliminate the use of hazardous starting materials and make the reaction to occur at moderate conditions Cyclization reaction

第154页：环氧丙烷的电合成

The electro-synthesis of epoxy propane（环氧丙烷）Unfortunately, the selectivity of this route is not as good as expected, and is not yet industrialized. Using electrochemical ways At the anode H 2 O-Na Cl

第155页：六氟环氧丙烷的电合成

• The synthesis of hex a flu oro propylene oxide 六氟环氧丙烷 F 2 CH=CFCF 3 Pb O 2/Steel/anode Steel/cathode H 2 O-HOAc-HNO 3 The conversion:65-75%, Selectivity:90%This route has already been industrialized by Hoechst Company Using electrochemical ways CF 3 CFCF 2 O

第156页：对苯二胺的电解合成

Using electrochemical ways

• The synthesis of para-diphenyl amine from 对苯二胺 ani line by electrolysis C 6 H 5 NH 2 H 2 O-NH 4 I/Pt NH 3 I-NH 2 NH 2-NH 2

第157页：对氨基苯酚的电合成

4 H++ O 2+4 e

• The electro synthesis of para-amino-phenol (PAP)对氨基苯酚 At the anode 2 H 2 OAt the cathode Using electrochemical ways C 6 H 5 NO 2+ 4 H++ 4 e+2 H 2 O

第158页：对苯二酚的电合成

• The electro synthesis of hydro chin one(hydro quin one, hydro quin ol)对苯二酚 At the anode C 6 H 6+2 H 2 O+ 6 H+At the cathode Using electrochemical ways C 6 H 6+ 2 H++ 2 e

第159页：光引发开环反应

• The cycle open reaction of dio x a ne (二恶烷)、O-or S-he t ero cy clo hexane (氧硫杂环已烷) use heavy metal catalyst traditionally, and additional reactants are needed.
• Ep ling etc use light as the reacting agent to realize these reaction and avoid the pollution caused by heavy metals Photo and other radiation conversion

第160页：光化学反应装置

第161页：2.5.5 安全有效的反应条件

2.5.5 Seeking for Safe and effective reaction conditions

第162页：催化剂与固体酸替代

• Seeking for safe and effective catalyst Loading of active component on suitable support more Replacing liquid acids by solid acids more
• Example 1
• Example 2
• Seeking for safe and effective reaction medium Using super critical fluid as reaction medium more Using water as reaction medium more
• Example 1（hydro for myl ation of propylene）

第163页：活性组分负载化

Loading of active components on suitable support

• Traditional Friedel-Crafts reactions：hydrofluoric acid(氢氟酸), sulfuric acid(硫酸), aluminium chloride(三氯化铝), boron fluoride(三氟化硼, boron trifluoride) are used as the catalysts. The disadvantages:

第164页：传统傅克反应的弊端

The disadvantages???

• What are the disadvantages of the traditional Friedel-Crafts reactions???

第165页：无水操作与腐蚀问题

• The operation must be done anhydrous ly(water free), 3 moles of hydrogen chloride will be released when accounting water.
• The system is corrosive, strict operation conditions must be controlled.
• Low selectivity because of the formation of poly-alkyl-substituted products and other isomers. Loading of active components on suitable support

第166页：酰基化反应的铝盐问题

• In a cy la tion reactions(酰基化)such as ordinary a cy la tion, the for myl ation of benzene(苯甲酰化), sulfo-a cy la tion(磺酰化),large amount of aluminium chloride is needed bec aue s of the complexity of the products.
• Finally, water must be added to release the product molecule and thus releasing large amount of hydrogen chloride as well as chlorinated hydrocarbons as impurity. Loading of active components on suitable support

第167页：蒙脱土负载催化剂

• The supported catalyst K 10-Al Cl 3，prepared by supporting Al Cl 3 on mont mori loni te(蒙脱土, im vite) shows activity as high as the conventional ones and higher selectivity for the formation of mono-alkyl a ted product than the old ones.
• The supporting of Zn Cl 2 on mont mori loni te (蒙脱土, im vite) could also obtain a new kind of catalyst for the Fri del-Crafts reactions, and this already provides a new perspective for industrial application. Loading of active components on suitable support

第168页：固体酸替代的利弊之问

Using solid acids to replace liquid acids What are the advantages and disadvantages of liquid acids catalyst ???

第169页：液体酸的优点

Using solid acids to replace liquid acids Advantages:

• Homogeneity
• Definitely known structure because of small molecules
• Easily investigation of the catalytic mechanism
• Mild reaction conditions

第170页：液体酸的缺点

Using solid acids to replace liquid acids Disadvantages:

• Low temperature: usually below 100℃
• Separation of the catalyst from the reaction mixture
• Cor rosi vit y and strict operation conditions
• Environmental pollution

第171页：固体酸的优势

Using solid acids to replace liquid acids Acidic clay(酸性白土), mixed chlorides, molecular sieve(分子筛) etc. could be used to replace liquid acids.

• （1）：Some inevitable barriers that could not be overcome in homogeneous catalysis could be lowered in a certain degree or totally overcome.
• （2）：The temperature range could be widened to 700-800 K, and thus widening the range of acid catalysis.

第172页：例1 傅克酰基化新催化剂

Example 1: The traditional Fri del-Crafts a cy la tion reaction: Target product/Aluminium chlo rode, 1/3 The use of new catalyst En vi roc at a. EPZG to replace Al Cl 3, the amount of catalyst could b

第173页：课堂练习

Problem Complete the reactions in example 1, compare their atom utilization and discuss their advantages and disadvantages.

第174页：超临界流体作为介质

Using super critical fluid (scf.) as reaction medium What is super critical fluid ?

第175页：超临界区相图

Supercritical Region Pressure Critical Point Temperature Pc Tc Liquid Vapour Solid 超临界区

第176页：超临界现象的发现

Baron C agni ard de la Tour Ann. Chim. 22410 (1822)

第177页：超临界相态变化

第178页：可视釜

View Cell

第179页：超临界萃取流程

第180页：清洁萃取工艺

Clean Extraction

第181页：超临界介质示意

第182页：超临界流体的特性

Using super critical fluid (scf.)as reaction medium

• The characteristics of scf: Cheap, safe and property adjustable. Scfs show different property under different conditions,we can adjust the super critical conditions to adjust its property until it satisfy our needs for the reaction to occur.

第183页：超临界二氧化碳的应用

Super critical carbon dioxide:

• Tanko used SCF CO 2 as the reaction medium for the brome substitution reaction of alky-substituted-aromatics , equivalent or higher yield and selectivity were obtained.
• Chemical Institute of guangzhou:
• SCF CO 2 was used as both the reaction medium and reactant in the carbonyl ation（羰基化）of olefin(烯烃)
• SCF water
• SCF water + carbon dioxide Using super critical fluid (scf.)as reaction medium

第184页：水相双相催化

Bi-phase catalysis using water as reaction medium

• Water-soluble complex compounds could be used as catalyst,and then the reaction takes place at the interface formed between the water phase and the organic phase of the reactants.

第185页：水相双相催化复页

Bi-phase catalysis using water as reaction medium

第186页：胶束的构建

• Micelle could be provided by varying the central atom and the ligand as well as the use of surf a cants,thus the interface could be enlarged and the regional concentration of the reactants could be increased.
• By varying the structure of the micelle, the stero-structure of the product could also be controlled. Bi-phase catalysis using water as reaction medium

第187页：双相催化的优势

• Thus, mild reaction conditions, high activity and selectivity could be afforded for and the separation of organic phase and water phase becomes easy. Meanwhile, environmental pollution could be avoided. Bi-phase catalysis using water as reaction medium

第188页：例2 苯与乙烯烷基化

Example 2：The alkyl ation of benzene with ethylene Forming ethyl benzene

• Traditional way: Al Cl 3, BF 3, HF were used as the catalysts
• Serious corrosion of the equipment
• Strict operation conditions
• Low yield
• Difficulties to eliminate HCl、RCl
• Difficulties of the separation of the catalyst and the products
• Waste water
• Hazardous HF used
• The use of phosphorus ZSM –5 molecular sieve overcomes the above shortcomings

第189页：双相催化新路线

Traditional way：Co-based catalyst, high pressure is needed Rh-or Pd-based water-soluble catalyst Bi-phase catalysis

第190页：李朝军教授介绍

Prof. Chao jun Li, Presidential Award of Green Chemistry, 2000, U. S. A, Canada Research Chair (Tier Ⅰ) in Green Chemistry Department of Chemistry Mc Gill University, Canada

第191页：2.6 绿色化学十二原则

2.6 Twelve Principles of Green Chemistry

第192页：十二原则索引

135791124681012

第193页：原则1 防止废物优于治理

1: It is better to prevent waste than to treat or clean up waste after it is formed

• Normal cost：
• starting material and reagent (intrinsic)
• the treatment and disposal of chemicals
• Large chemical companies in U. S.:
• expenditures on research and development ≈expenditures on environmental health and safety
• The costs of dealing with hazardous substances, either through handling, treatment, or disposal, have continued to increase substantially

第194页：原则1 风险判据

1: It is better to prevent waste than to treat or clean up waste after it is formed

• A criterion that is often assessed to calculate the need or desire for treatment or control of a chemical substance is whether or not damage has been done by the generation of waste.
• In many cases the “damage” is merely that substances have been uselessly processed or transformed, costing energy, money, time for separation from product, and almost always requiring technology to get rid of them or to render them innocuous.

第195页：原则1 未转化原料

1: It is better to prevent waste than to treat or clean up waste after it is formed

• One type of waste production that is both common and often the most avoidable is starting material or reagent that is un converted.
• When one wastes starting material, one is paying for the substance twice; once as a feedstock and again as a waste and so one has achieved no utility from the substance. More seriously, often the cost of waste disposal may be many times the cost of the virgin starting material.
• Thus, if possible, it is better to cut pollution from its origin rather it is formed.

第196页：原则2 最大化进入产物

2: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product

• The classic evaluation of the effectiveness and efficiency of a synthesis is“Yield”.
• This“Yield”totally ignores the use or

第197页：重排反应

• Atomic ally economy reactions
• Rearrangements
• By definition, a rearrangement reaction is are organization of the atoms that make up the“old”molecule. Thus all atoms in the reactants are incorporated into the product.
• Addition reactions

第198页：取代反应

• Non atomic economical reactions
• Substitution
• Because in this kind of reaction, one group(the substituting group) displaces a leaving group, the leaving group is necessary a waste product of the reaction that is not included in the final product and therefore diminishes the atom economy of the transformation. The exact

第199页：消除反应

• Elimination
• Elimination reactions transform the substrate by reducing the atoms to generate the final product.
• The eliminated atoms are lost as waste.2: Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product

第200页：原则3 降低危害

3: Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment

• The fundamental basis of green chemistry is the incorporation of hazard minimization or elimination into all aspects of the design of the chemistry.
• Green chemistry recognizes that it is through the skills and knowledge possessed by chemists that today’s world can have the modern technological advances that have come to be expected from the scientific community in a way that is safe for human health and the environment.

第201页：原则3 减少暴露

3: Wherever practicable, synthetic methodologies should be designed touse and generate substances that possess little or no toxicity to human health and the environment

• There are only two ways to minimize risk of harm of any kind:
• Minimize the exposure
• A variety of forms could be taken: protective clothing, engineering control, respirators etc.
• It is virtually impossible to control exposure without increasing the cost of the process.
• Exposure controls can fail, and so ones risk increases commensurate ly with that failure.
• Minimize the hazard
• The intrinsic characteristics that is not going to change and therefore the risk will not increase spontaneously.

第202页：原则3 现实的理由

3: Wherever practicable, synthetic methodologies should be designed touse and generate substances that possess little or no toxicity to human health and the environment

• Multi-fold pragmatic reasons for necessarily considering the hazard:
• It is impossible to control exposure without increasing the cost of the process
• Exposure controls can fail and so ones risk increases commensurate ly with that failure.
• We can consider
• We have no other choice

第203页：原则4 保持功效降低毒性

4: Chemical products should be designed to preserve efficacy of function while reducing toxicity

• Designing safer chemicals Through the knowledge of the molecular structure, chemists can obviously determine quite a bit about the characteristics of the compounds.
• Why it is possible to design safer chemicals?

第204页：安全化学品设计途径

Ways of designing safer chemicals If a certain reaction is essential for the toxic mechanism to be carried out, a structural change could be made to ensure that the reaction could not take place. Of c

第205页：构效相关的设计

If the mechanism is not known, looking for the correlation existed between chemical structure and the existence of toxic effect. The functionality related to the toxic effect would be avoided, minimiz

第206页：原则5 减少辅助物质

5: The use of auxiliary substances(e.g.solvents, separation agents) should be made unnecessary wherever possible and innocuous when used

• Challenges facing the use of auxiliary substances
• auxiliary substances are generally used
• Concerns for solvents
• Effects of solvents on the environment
• How to eliminate auxiliary substance
• Super critical fluids （超临界流体）
• Solvent less（非溶剂化）
• Aqueous (水作溶剂)
• Im mob liz ed (固定化)

第207页：原则6 能源需求

6: Energy requirements should be recognized for their environmental and economical impacts and should be minimized

• Energy is widely used in chemical industry Energy generation and consumption has long been known to include a major environmental effect.

第208页：能源的使用方式

Energy requirements should be recognized for their environmental and economical impacts and should be minimized

• How energy is used in chemistry and chemical industry?
• Pre-heating of the reaction mixture
• Accelerating the reaction rate with heat

第209页：能耗的优化

Energy requirements should be recognized for their environmental and economical impacts and should be minimized

• Optimizing the reaction conditions to minimize the energy requirements
• In the past The process engineer balance the energy requirements
• Nowadays The chemist who designs the reaction has the

第210页：原则7 可再生原料

7: A raw material or feed stock should be renewable rather than depleting, wherever technically and economically practicable

• The difference between “renewable resources ”and “depleting ones”is described simply by “time”
• “Depleting resources”are usually thought of as the fossil fuels.

第211页：化石燃料的时间尺度

• Except for the fact that it would require millions of years to occur, fossil fuels could be accurately described as renewable inasmuch as vegetation could once again be converted to petroleum. Since this is not generally thought of as practical, fossil fuels are considered depleting.7: A raw material or feed stock should be renewable rather than depleting, wherever technically and economically practicable

第212页：太阳与太阳能

• One of the true depleting resources we have is the Sun and solar power but that is again subject to the criterion of time. Since the Sun will last millions of years, it is often referred to as an infinite supply of energy, although, unlike fossil fuels, once it is exhausted it will never be replenished.7: A raw material or feed stock should be renewable rather than depleting, wherever technically and economically practicable

第213页：可再生原料的来源

• Renewable feed-stocks are most often associated with biological and plant based starting materials.
• The term, however, can be equally applied to substances that are easily regenerated within time frames that are accessible to the human lifetime.
• Carbon dioxide, methane 7: A raw material or feed stock should be renewable rather than depleting, wherever technically and economically practicable

第214页：原则8 减少不必要的衍生

8: Unnecessary derivations (blocking group, protection/de protection,temporary modification of physical/chemical processes)should be avoided whenever possible

• Challenges faced by chemical synthesis and their green chemical solutions
• Target molecules become more and more complex;
• Stereo-control, effecting a reaction in the

第215页：保护基团

• Blocking/protecting groups
• Blocking, or protecting groups are used to protect a sensitive moiety from the conditions of the reaction, which may jeopardize the functionality if it is left un protected.
• -OH,-NH 28: Unnecessary derivations (blocking group, protection/de protection,temporary modification of physical/chemical processes)should be avoided

第216页：成盐处理

• Making salts
• It is common that certain substances need to be formulated or blended with other substances in order to effect their macro or performance properties, such as viscosity, disp ers ability, vapor pressure, polar iz ability, water solubility etc..8: Unnecessary derivations (blocking group, protection/de protection,

第217页：官能团的临时引入

• Adding a functional group only to replace it
• Several reactive sites existed in a molecule
• Activate certain site 8: Unnecessary derivations (blocking group, protection/de protection,temporary modification of physical/chemical processes)should be avoided whenever possible

第218页：原则9 催化优于计量

9: Catalytic reagent (as selective as possible) are superior to stoic hio metric reagents With stoic hio metric reactions:

• One of the starting material, A or B, is a limiting reagent and therefore there will be un reacted starting material left over even in a reaction with 100% yield.
• One or both of the starting materials are only partially needed for the end-product and so the balance of the molecules go to the waste stream; or
• Additional reagents are needed to carry out or facilitate the reaction and those reagents will need to be discarded in the waste stream when the reaction is completed.

第219页：催化的作用

• The obvious effect of catalysis to facilitate the reaction:
• Enhance the selectivity
• Minimize the energy costs 9: Catalytic reagent (as selective as possible) are superior to stoic hio metric reagents

第220页：原则10 可降解设计

10: Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products

• Persistent chemicals (such as plastic)/persistent bio accumulators
• Plastics Durability and long life were required before
• Pesticides Organ oho loge n structure

第221页：降解即功能

• Just as you design for function, consider degradation as a function
• Designing for biodegradability 10: Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products

第222页：原则11 实时分析

11: Analytical methodologies need to be developed to allow for real time, in-process monitoring, and control prior tothe formation of hazardous sub at ances

• You can not control what you cannot measure
• Accurate and reliable sensors, monitors, and analytical techniques are needed to asses the hazards that are present in the process stream.
• In-process and in-real-time techniques(in situ) are needed，
• Determine the completion of the reaction

第223页：原则12 防止事故

12: Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires

• Accident prevention should be considered
• Consider the balance of the prevention of both pollution and accidents

第224页：固体与低蒸气压物质

• The use of solids or low vapor pressure substances
• The realization of “just-in-time” techniques involve the generation and rapid consumption of hazardous substances within a contained process.12: Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires

第225页：主要参考文献

主要参考文献

第226页：参考文献（一）

1.吴毓林，陈耀全，化学迈向辉煌的新世纪，化学通报，1999，1：3-92.杨宏秀 21 世纪的化工发展趁势，化学通报，1999，10：39-423. Paul T. Anastas, Tracy C. Williamson, Green Chemistry—designing chemistry for the environment, American Chemical Society, 19964.美国国家研究委员会，化学科学与技术部

• 催化科学技术新方向专家组，熊国兴，陈德安译，催化展望，北京大学出版社，19935.《绿色化学的基本科学问题》九华论坛纪要，1999，12

第227页：参考文献（二）

• 6. Paul T. Anastas, Green Chemistry, Theory and Practice, Oxford University Press,19987. Paul T. Anastas, Tracy. C. Williamson. Green Chemistry, Frontiersin Benign Chemical Synthesisand Processes, Oxford University Press,19988. Stephen C. Devito and Roger L. Carre tt, Design ig Safer Chemicals, American Chemical Society,19969.朱清时，绿色化学的进展，大学化学，1997，12（6）：7-11]
• 10. 朱清时，绿色化学和新的产业革命，现代化工，1998，1：4-6

第228页：参考文献（三）

11 闵恩泽，傅军，绿色化学的进展，化学通报，1999，1：10-1512 段启伟，闵恩泽，何鸣元，绿色技术在石油化工中的应用研究进展，石油化工，2000，29（7）：530-53413 Kazuhiko Sato, Masao Aoki, Ryoji Noyri, A Green Route to Adi pic Acid: Direct Oxidation of Cy clo hexane s

第229页：参考文献（四）

14 K. M. Dra th s, J. W. Frost,synthesis using Plasmid-Based Bio catalysis: Plasmid Assembly and 3-Deoxy-D-arabi no-he pt u los c nate，J. AM. Chem. Soc.1990.112:1657-1659.15 K. M. Dra th s J. W. Frost

第230页：参考文献（五）

• 17. 朱清时，化学的绿色化和绿色植物的化学转化，绿色化学，中国科学技术大学出版社，1998。
• 18. Life ng Yan, Qing shi Zhu, and To miki Ikeda, Ethyl cellulose films as Alignment Layers for liquid crysta Ls,绿色化学第三届国际高级研讨会论文摘要集，2000，104-108。
• 19. Yu zhong Zhang, Jie Liu and Peiji Gao, Exploring the super strut ure of naru re cellulose and its structural changes during bio de gad ation by STM approach, 绿色化学第三届国际高级研讨会论文摘要集，2000，109-120。

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• 20. 朱清时，阎立峰，单分子生物多糖力学性能的 AFM 研究，绿色化学第三届国际高级研讨会论文摘要集，2000，163-167。
• 21. 谢君，任路，刘尚旭，余风燕、董佳里，张义正，白腐菌产生木质纤维素降解酶的研究，绿色化学第三届国际高级研讨会论文摘要集，2000，168-172。
• 22. 刘尚旭，董佳里，张义正，新的木质素降解酶产生菌的筛选，绿色化学第三届国际高级研讨会论文摘要集，2000，177-180。
• 23. Paul A. Wender, Introduction: Frontier in Organic Synthesis, Chemical Review,1996,96(1):1-224. Barry M. Trost, The Atom Economy-A Search for Synthesis Efficiency, Science 1991,254:1471-1477.

第232页：参考文献（七）

25 曾庭英、宋心琦，化学家应是“环境”的朋友——介绍绿色化学工艺，大学化学，1995，10（6）：25-31。

26 刘昌俊，张悝，许根慧，催化等离子体合成燃料油及与费耗合成的比较，第七届全国青年催化学术会议论文集，1999，439-440。

27 黄培强，高景星，绿色合成：一个逐步形成的学科前沿，化学进展，1998，10（3）：265-272。

28 吴越，取代硫酸、氢氟酸等液体酸催化剂的途径，化学进展，1998，10（2）：158-171。

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• 29. Jocelyn Kaiser, Super critical Solvent Comes Into Its Own, Science, 1996:158-171.
• 30. 陈华，黎耀忠，李东文，程溥明，李贤均，化学进展，1998；10（2）：146-157。
• 31. 李贤均, 陈华, 黎耀忠, Molecule Assembly in Mi cellar Interface and High Regio selectivity of Ole fen Hydra for myl ation in Bie has ic Catalytic System, 4 th Annual Green Chemistry and Engineering Conference, Washington D. C., USA.2000.3

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• 32. Paul t. Anastas, Lauren B. Bart lt t, Marry M. Kirchhoff, Tracy C. Williamson, The role of catalysis in the design, development, and implementation of green chemistry, catalysis Today, 2000, 55:11-22.
• 33. Roger A. Sheldon, Organic Synthesis—Past, Present and Future, Chemistry&Industry,1992,(7, Dec.)：903-906.
• 34. Barry M. Trost, The Atom Economy–A Search for Synthetic Efficiency, Science,1991,254：1471-1477.

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• 35. Barry M. Trost, A biological Catalysis for Synthetic efficiency, Pure & Appl. Chem, 1992, 64(3):315-322.
• 36. A. Maureen Rouhi, Atom economical reactions help chemists eliminate waste, C & EN, 1995, (June 19): 32-35.

第236页：本章作业（上）

本章作业

• 1：简答。绿色化学的目标、化学工业造成的危害、风险试剂、生物质的种类、可再生资源原子利用率、环境商、环境因子
• 2：为什么要大力发展绿色化学？
• 3：绿色化学及其与环境污染治理的异同。

第237页：本章作业（中）

• 4：什么是绿色化学品？怎样设计安全的化学品。
• 5：举例说明原子经济反应是不产生污染的必要条件。
• 6：试论计算机辅助绿色化学合成路线设计的必要性和方法。
• 7：怎样在反应过程中使化学反应绿色化。本章作业

第238页：本章作业（下）

• 8:试论分析化学在绿色化学发展中的作为。
• 9：简述绿色化学 12 原则。
• 开卷考试题：自选一条目前使用的有机化学合成路线，用绿色化学原理对其进行评价并设计一条更佳的新路线。本章作业