05 第五章 绿色化学方法.ppt

第1页：第五章 绿色化学中的技术

Chapter 5 Techniques in Green Chemistry

第2页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第3页：5.1 催化剂在反应中的作用

5.1 The performance of Catalysts in Chemical reaction

第4页：催化剂应用实例

Samples for the Application of Catalysts Noreactantsproductscatalyst T/Kp/MPa phase The role of catalyst 11/2 N 2＋3/2 H 2 NH 3 Fe-K 2 O/Al 2 O 372340.53 Gas-solid Accelerate reaction rate 2 a C 2 H 4＋

第5页：催化剂应用实例（续一）

2 b C 2 H 4＋1/2 O 2 C 2 H 4 OAg/Al 2 O 35200.1013 gas-solid 2 c C 2 H 4＋3 O 22 CO 2＋2 H 2 ONi 5200.1013 Gas-solid 3 an C 3 H 6[C 3 H 6]n O 2420~450202.6 gas 3 bn C 3 H 6[C 3 H 6]n Cr 2 O 3

• Si O 2
• Al 2 O 3 or MO 3
• Al 2 O 3420~4503.1 Gas-solid -liquid 3 cn C 3 H 6[C 3 H 6]n Ziegler-Natta 3730.1013 Gas-solid -liquid 42-(6-甲氧基-2 萘基)丙烯酸＋氢左旋二羟基苯丙氨酸(L-n apr oxen) Ru Gas-solid -liquid

第6页：催化剂应用实例（续二）

5 a CH 3 CH 2 OHC 2 H 4＋H 2 OAl 2 O 3623~683 Gas,solid Controlthe Selectivityfordifferentproducts 5 b CH 3 CH 2 OH（C 2 H 5）2 O＋H 2 OAl 2 O 3523 Gas,solid 6 a CH 4＋O 2 CO＋H 2 Ni/Al 2 O 3673~12730.1013~

第7页：催化剂的两类作用

The application of catalysts to chemical reaction

• Accelerate the chemical reaction rate
• Accelerate selectively the one of the several thermodynamic ally possible reactions and yield selectively the special products.
• Namely, the use of catalysts can control the selectivity for special products.
• Control the en anti o selectivity of reaction

第8页：手性构型的合成

• Synthesize the special conformation of chiral isomers
• Incorporate with reaction conditions, and control the selectivity of chemical reaction. Catalyst has been called as molecular machine
• It is the most important of high selectivity and atom economy in bios-process, and all the reactions in biomass are catalyzed by enzyme.
• high specific i ties, selectivity and atom economy.

第9页：分子机器的比喻

Catalyst has been called as molecular machine Hence, those enzyme have been called as Molecular Machine ADP ATP ATP ADP ADP ATPADP+Pi ATP ADP A hand-over-hand mechanism for kin es in

第10页：普通催化剂的类似功能

• Recent investigations have reported that not only enzyme acts as molecular machine but also the common catalysts own the similar functions.
• The classical example is the metal cyclopentadiene(环戊二烯) complex which was used as the catalyst in olefin polymerization Catalyst has been called as molecular machine

第11页：齐格勒-纳塔催化剂

continue Ziegler-Natt a catalyst: me ch n sim? 。

第12页：齐格勒-纳塔机理

第13页：酶与传统催化剂

• Enzymeandothertraditionalchemicalcatalyst.
• If they exhibit high specificity,selectivity,yield and atom economy,theyshouldbeconsideredasthemolecularmachinewithspecialfunctionsinchemicalreactions. Catalyst has been called as molecular machine

第14页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第15页：5.2 绿色化学与催化

5.2 Green Chemistry and Catalysis

第16页：催化的三项作用

Catalysis and Pollution Protection The activation of new starting materials Catalysis and Process Promotion

第17页：催化与污染防护

Catalysis and Pollution Protection

第18页：减少氮氧化物排放

• Catalysis plays a important role in pollution protection
• Catalysis can decrease and eliminate the release of NOxin exhaust form cars and factories，and improve the air quality. High Temperature, NOX. Load catalyst Lower Temperature

第19页：减少挥发性溶剂

• Catalysis plays a important role in pollution protection
• Catalysis can decrease the usages of volatile organic solvents
• Catalysis can substitute the synthesize methods and process composed of chlorine materials and intermediates, and decrease the formation of wastes.

第20页：无污染的新路线

Catalysis plays a important role in newly synthesize route without pollution The chemical reaction may become more effective and more selective over catalyst, which can decrease the formation of by-pr

第21页：新原料的活化

The activation of new starting materials

第22页：邻苯二酚的传统合成

The synthesis of cat echo l Traditionally: Benzene is harmful，Too many steps，By-products (ket ene hydro quin one)，SO 2 is not safe chemicals,continue

第23页：葡萄糖路线

Dra th s & Frost glucose as starting martial Avoidtheusageoftoxicandharmfulchemicalsandsharplydecreasetheyieldofby-products.

第24页：催化与过程强化

3. Catalysis and Process Promotion

第25页：乙醛的合成

CH 2=CH 2 O 2 Pd Cl 2 Cu Cl 2 水溶液 CH 3 CHO Disadvantages: Consume large amount of catalysts The consternation of Cl-is greater, and can lead to the formation of chromate by-products. Those by-products is harmful to human healthy

• 1. The synthesis of acetic aldehyde

第26页：对苯二酚的传统法

2. The synthesis of hydro chin one Traditional Method：Disadvantage:too many steps, a large mount of by-product,corrosive ch mic als (H 2 SO 4, HCl)

第27页：环境友好的新法

Environmental beige n method: Advantages: Greener method: Short reaction chain，By-products only formatted in the final step.

第28页：羰基化合物的合成

R 1 C(OH) R 2 R 1 COR 2 cat.microwave Varma et al: the activation under microwave and catalyst Traditionally Organicsolvent; Cr O 3, KMn O 4; Slat pollution The synthesis of carbonyl compounds

第29页：生物质的催化转化

Conversion of Biomass Bamboos Small Molecules Such as: CH 3 COOH, CH 3 OH etc New Catalysts

第30页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第31页：5.3 高效安全催化剂的设计

5.3 The Design of High Efficient and Safe Catalyst

第32页：总体分析的内容

1: Gross analysis 1. At first,analyses:

• thepossibilityofreactionandthelargestequilibriumyelid
• the optimized reaction condition
• the available martial s
• atomeconomyofreactioninrealreaction
• economy of catalysts
• economy

第33页：催化剂设计的参数

• 2. Severalfactorsshouldbeconsideredtodesignparametersofcatalysts.activity,selectivity,stability,duration and toxicity,etc
• 3. According to the reaction routes,search the catalyst and

第34页：清洁氧化剂的需求

2.design and develop the new type molecule oxygen oxidative catalysts Traditional inorganic oxidants：

• Na Cl O, Na Br O, HNO 3, KHSO 3,
• Cr O 3, KMn O 4, KCr 2 O 7,etc. The traditional inorganic oxidative can introduce a large amount of
• waste salts, hazardous gases and liquids
• heavy atoms

第35页：氧气是最清洁的氧化剂

• O 2:
• The cleanest oxidative chemical
• The limitation of its reaction conditions,
• Often com pani ed by other auxiliary oxidants Clean oxidative and their characters

第36页：过氧化氢

Clean oxidative and their characters

• H 2 O 2 H 2 O 2 contain more than 47 percent active oxygen, and its oxidative products (water) is environmental benign chemical. H 2 O 2 is more expensive than O 2 and O 3, and can d is corporate in room temperature

第37页：臭氧

• (O 3)：
• O 3 is also the environmental benign chemical oxidative, and its oxidative products is oxygen molecule. But the usage of O 3 often require some special method and equipments. Clean oxidative and their character s O 3 tube transformer

第38页：氧化亚氮

• (N 2 O)：
• its oxidative products is environmental benign product (N 2)
• the synthesis of N 2 O is complex and the cost of N 2 O is very high. Clean oxidative and their characters

第39页：基于机理的设计

Design of oxidative catalyst based on the reaction mechanism

• Thereactionmechanismofdifferentreactionsystem,including catalysts，may vary.
• Hence,therequirementsforcatalystsshouldalsobedifferent.
• Thedesignofcatalystsshouldbetoughlyconsideredthereactionmechanismtomeettherequirementofreaction.

第40页：新型金属配合物催化剂

3、The design of new-type metal complex catalysts

第41页：金属配合物的应用

Metal complexes

• Those metal-organicscatalystsarewidelyusedinhomogenouscatalyticreactions
• Chiralmetalcomplexeshavebeenusedashomogenouscatalyst，and can control the stereo-selectivity of the reaction.
• It is very important for high stereo-selectivitytosearchthesuitablereactionconditionscentralme,propercentralmetalionsandchitalgroups.

第42页：萘普生的合成

Sample：the synthesis of N apr oxen The yield of target product (S-N apr oxen) reaches 97%。

第43页：表5-2 工业金属配合物

Table 5-2 Some metal complexes in industry Chiralcomplesx Indoctrinationtime Ru BINAPAminehydrogenation 1991 Ru BIN AP chino i line 1987（Iso quin ol alkaloid）Ru BINAPTerpenealcoholhydrogenation 1987 R

第44页：分子筛催化剂

4, Designing of New Molecular Sieve Catalyst

• Molecular Sieve(分子筛) Molecular sieve refers to a kind of inorganic polymer composed of aluminum silicate (silicon alumina te), bearing open structure.

第45页：分子筛的结构单元

• Structurally,molecular sieve bears the tetra-XO 4 structure, in which one atom X shares O with other X atoms. X may be tri-(Al, B, or Ga), tetra (Ge, Si)-, or penta-(P) valent. Designing of New Molecular Sieve Catalyst

第46页：孔径与分类

Designing of New Molecular Sieve Catalyst

• The pore diameter of molecular sieve is dependant on the number of building units, and the molecular sieve is generally named macro-, meso-, or micro-molecular sieve corresponded respectively to the mean pore diameter of 0.75, 0.67 or 0.43 nm.

第47页：天然与合成沸石

• Natural Molecular Sieve（Zeo lite）iswidelyusedinpetrolrefineryforitsmacroporestructure.
• Synthesizedzeoliteisnowcommercializedandhasbecomeoneofthemostimportantcatalystinpetrolindustry. Designing of New Molecular Sieve Catalyst

第48页：分子筛孔道结构

第49页：丁烯烷基化的传统法

The alkyl at tion of butene：Traditional method：HF and/or H 2 SO 4 are used as the catalysts. Advantage:

• high efficiency Disadvantages:erosion of HF/H 2 SO 4production of inorganic saltsHF could be recycled, but H 2 SO 4 could not and should be removed.

第50页：固体分子筛酸催化剂

the use of solid molecular sieve acid catalyst：

• Theerosionofliquidacidiseliminated，
• Noinorganicsaltsaswastesproduced. Solid acid catalyst

第51页：分子筛的碱性催化

Molecular Sieve could also be used as basic catalysts or acidic-basic bi functional catalyst

• already used for the production of fundamental chemicals but not as widely as acid catalysts
• It will undoubtedly play an important role in the production of fine chemicals and special chemicals. For example, Cs Molecular sieve is used in the synthesis of 4-methyl-thi a zo line(4-甲基噻啉，one kind of anti-fungus) instead of Cl 2 or CS 2 and Na OH.

第52页：形状选择性

Changing the selectivity of a chemical reaction originated from the shape of molecular sieve by chemical modification of molecular sieve

• The selectivity of chemical reactions based on the shape of the molecular sieve could be altered by chemical modification of the molecular sieve used as the catalysts, this provides wide applications of molecular sieve in controlling chemical reactions.

第53页：二异丙基萘的合成

For Example

• In the synthesis of 2,6-di-isopropyl naphthalene, a mixture of 2,6-, 2,7-, and 2,4-substituted naphthalene is obtained using ordinary methods.2,4-di-isopropyl naphthalene+2,7-di-isopropyl naphthalene 2,6-di-isopropyl naphthalene

第54页：传统催化剂的局限

• The traditionally used catalyst Si O 2/Al 2 O 3 has large pores, and could not distinguish 3-substituted-isopropyl naphthalene from 4-substituted-isopropyl naphthalene, and the distinguish of 2,6-di-isopropyl naphthalene from 2,7-di-isopropyl naphthalene could neither be realized.
• The separation of 2,6-di-isopropyl naphthalene and 2,7-di-isopropyl naphthalene by using special polymer liquid crystal is very troublesome and very expensive. For Example

第55页：小孔分子筛的作用

• The use of small pore molecular sieve could inhibit the formation of 3-, or 4-, substituted products but the formation of equivalent amount of 2,6-and 2,7-substituted products could not be avoided.
• The formation of 3-and 4-substituted products could be eliminated, and a ratio of 2,6-to 2,7-substituted products of 7/3 could be obtained by using Zeo lite-C as the catalyst.
• Table 5-3 gives out the distribution of products by using different kinds of catalysts. For Example

第56页：表5-3 产物分布

Table 5-3，The distribution of the products from the alkyl ation of naphthalene by using different kinds of catalysts Catalyst Pore diameter / nm 2, 6-/2, 7-2,6-isomer %Si O 2/Al 2 O 36.0132 L-molecula

第57页：分子筛催化剂的展望

Prospect for the research of molecular sieve catalysts

• Molecular sieve catalysts may replace such substance as HF, H 2 SO 4, etc., which are obviously dangerous to people’s health and the environment. Thus, molecular sieve catalyst is regarded as one kind of environmentally benign catalyst.
• Simultaneously, on account of the significant increase of the activity and selectivity due to the use of molecular sieve catalyst, the research of molecular sieve catalyst will undoubtedly become one of the most promising field in green chemistry.

第58页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第59页：5.4 变更起始原料

5.4 Changing Starting Material for Chemical Reaction

第60页：原料选择的重要性

Selection of starting materials

• The feedstock has great influence on the efficiency of the synthetic routes, on the environmental effects and the healthy of human beings.
• The hazard of feedstock must be considered by the producers, managers in the preservation and transportation, as well as the operators in the processing.
• For some bulk chemicals, the change of feedstock may change the market, for some substance are produced just to provide certain feedstock.

第61页：降低危害性的评估

1. Reducing hazardous properties(1). Certainly, a first level assessment of any starting material must be

• whether the substance itself is benign;
• whether it poses a hazard for human beings and for the environments;
• whether it poses a hazard in the form of either toxicity, accident potential, ecosystem destruction, or other form;
• whether it is destructive for the ecological environment
• whether it poses other un-benign properties

第62页：优选原料来源

(2). Using preferable sources

• Currently, more than 90% organic starting materials are almost exclusively derived from non-renewable carbon feedstocks, such as coal or crude oil.
• Petrol-refinery is energy consuming. For example, in the U. S., the amount of energy consumed in petrol-refinery is about 15% of its energy consumption. The cost will augment for the quality of the crude oil is becoming bad.
• In the production of organic chemicals from oil, oxidation reactions are usually employed, and it is well known that oxidation reactions are seriously pollutant.

第63页：减少对化石资源的依赖

using preferable sources

• Considering the use up of oil, natural gas and coal, we must reduce our dependence on these fossil resources.
• Agriculture resources and bio-resources are good alternative. Recent studies show that, many agriculture resources, such as corn, potato, soybean, and so on could be converted to textiles or nylon. Agriculture waste, biomass containing cellulose and lignin could also be converted to chemicals.

第64页：生物质的优势一

• 2. Advantages and disadvantages of biomass as a chemical feedstock
• (1). Advantages advantages
• biomass can be broke down into a huge array of structurally diverse materials, frequently stereo chemically and enantiomeric ally defined, giving the user a wide range of new structural features to exploit in synthesis.

第65页：结构复杂性的优势

• The structural complexity of the building blocks available from biomass is frequently higher when compared to building blocks derived from petrochemicals. This property could lead to a reduction of reaction side

第66页：含氧结构的优势

• Building blocks isolated from crude oil are not oxygenated, yet many of the final products of the chemical industry are. There are few ways to add oxygen to hydrocarbons,and many of them require the use of toxic

第67页：延长石油资源的寿命

• Increased use of biomass would extend the lifetime of the available crude oil supplies, and then make contribution to sustainable development and make sure the production of certain chemicals that could only be synthesized from oil.
• The use of biomass has been suggested as a way to mitigate the buildup of greenhouse CO 2 in the atmosphere. Since biomass uses CO 2 for growth through photosynthesis, the use of biomass as a feedstock results in no net increase in atmospheric CO 2 content when the products break down in the environment.advantages

第68页：原料供应的安全

• A chemicals industry incorporating a significant percentage of renewable materials is secure because the feedstock supplies are domestic, leading to a lessened dependence on international ‘hot spots’ .advantages

第69页：原料的灵活性

• Biomass is a more flexible feedstock than is crude oil. Crude oil is formed and its composition set by geological forces. The diversity of building blocks from biomass offers a great opportunity for the production of a range of chemicals as wide as that available from non-renewables. With the advent of genetic engineering, the tailoring of certain plants to produce high levels of specific chemicals is also possible.advantages

第70页：生物质的劣势一

• （2）、disadvantages
• Many of the reported disadvantages are related to current economic circumstances. The petrochemical industry is huge and highly efficient, from the initial removal of crude oil, to the extraction of the simpler building blocks that comprise the crude oil, through the final transformation of these building blocks into their many intermediates and chemical products. Moreover, the petrochemical industry is well established. Much of its capital investment is paid off. The mechanisms and operation of its processes are well understood and give single products of high purity. The biomass industry is still developing processes that possess these features.disadvantages

第71页：与粮食的竞争

• Many of the biomass sources being considered as chemical feedstocks have traditionally been used as sources of food, and the justification for diverting part of this resource to chemical production has been questioned. The issue becomes more acute when biomass is considered as a feedstock for fuel as well as chemical production. Biomass also requires space to grow, and the environmental impact of large scale biomass plantations has been examined.disadvantages

第72页：三维结构的难度

• Traditional sources of chemical feedstocks have been referred to as ‘three dimensional’ because the structures in which they are found have depth as well as length and width. The presence of the third dimension allows much more feedstock to be concentrated in a smaller area. In contrast, biomass feedstocks are ‘two dimensional’ feedstocks, and require proportionally more space for the same amount of material.disadvantages

第73页：季节性问题

• Biomass is necessarily seasonal. The crop is planted in one part of the year, and harvested in another. This leads to peaks and valleys in the supply of feedstock; yet the chemical producer planning to use biomass needs a regular day to day supply, and needs to be assured that the material used at the beginning of the year will be of the same quality as that used at the end of the year.disadvantages

第74页：成分多样的挑战

• The wide range of materials that comprise biomass could be a detriment especially if new processes need to be developed for each feedstock. Moreover, the building blocks extracted from biomass are foreign to traditional chemical producers and must be demonstrated to function in a manner similar to existing building blocks without undue manipulation.disadvantages

第75页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第76页：5.5 变更试剂

5.5 Changing Reagents

第77页：试剂改进的方向

Selection of reagents Many progress have been achieved in this aspect on green chemistry For example：Using light instead of some reagents; Using recoverable catalyst as it is possible; Loading the rea

第78页：叔烃氧化为酮

Selection of reagents For example, for the oxidation of tertiary hydrocarbons to ketone s, the traditional method involves the reaction of copper acetate and hydrogen peroxide in the aqueous solution,

第79页：溶剂是否必要

5.6 Changing reaction solvent Is solvent necessary for the reaction?

第80页：溶剂体系的替代

• Aqueous solution system
• Ionic liquid
• Immobilization of the solvent——Solution of polymer
• Carrying out polymerization reactions using the solvent as one of the monomer to obtain polymer i zed-solvent-der i vates that bear the property of the solvent. Since this solvent is anchored on the polymer, thus the separation of the products from the solvent is eliminated and pollution from the volatile solvent is also eliminated.

第81页：无溶剂反应

Solvent-free reaction

• Band ger et al combine the use of environmentally benign catalyst and microwave to synthesis 3-carb in yl-co umar in from di-me thy oxy benz aldehyde and Mel drum acid without using solvent. The combination of microwave and catalyst instead of solvent is effective in such processes as group protection, de protection, oxidation, reduction, rearrangement reaction.

第82页：超临界区相图

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

第83页：超临界二氧化碳的形成

Formation of SCF CO 2

第84页：超临界二氧化碳形成复页

Formation of SCF CO 2

第85页：超临界流体的传递特性

Transmission characters of S CFS CF:

• Density: Similar to liquid;
• Viscosity: 1/100 than liquid:
• Liquidity: much better than liquid
• Reynolds number: much better than liquid (same current velocity) 。
• Transfer coefficient: much better than liquid;

第86页：黏度与温度的关系

Newton Formulaμ=τyx/dμx/dy With temperature increasing,for gas: Viscosity increases for liquid: Viscosity decreases. SCF: Itsviscosityisnotequaltothatofliquidorgas. Butitisliabletothatofliquid Viscosi

第87页：偏摩尔体积

Partial molar volume

• In SCF，the partial molar volume of infinite dilution solute is negative
• Near the critical region, it will further become more negative (about -1000∼16000 ml/mol)

第88页：超临界流体的优势一

Advantages of SCF in chemical reaction solvent

• 1. Itisconvenienttoadjusttheprosperityof SCFfromlikegas-like phase to liquid-likephaseintermofcontrollingpressure. That is to say,thecontrolofpressurecanaltertheprosperityof SCF,whichmakesthereactionbecomemoreeffective.
• 2. Thecontrolofpressurecanadjustthedensityof SCF,andcanalsoadjustotherpropertiesrelatedwithdensity,suchasdialecticconstantandviscosity,whichpromotethepossibilitiestocontrolreactionandtoincreasesthereactiveselectivity.
• 3. SCFalsoowncharacteristicslikesomegases,such a slow viscosity,large diffusion coefficient,whichismuchimportanttoacceleratethereactionrate,especiallytothosereactionsincludinggaseousreactants.

第89页：不可燃的优势

• Another advantage of non-ox i diz ability for SCF CO 2 makes it become an ideal reaction solvent.
• The high concentration of CO 2 in SCF CO 2 make it liable to react in its SCF condition, which accelerate the reaction rate and make some reaction to occur. Advantages of SCF in chemical reaction solvent

第90页：第五章 章节导航

Chapter 5 Techniques in Green Chemistry

• 5.1 The performance of Catalysts in Chemical reaction
• 5.2 Green Chemistry and Catalysis
• 5.3 The Design of High Efficient and Safe Catalyst
• 5.4 Changing Starting Material for Chemical reaction
• 5.5 Changing Reagents
• 5.6 Changing the solvent of Chemical Reaction
• 5.7 Process Control and Process Intensification
• References

第91页：5.7 过程控制与过程强化

5.7 Process Control and Process Intensification

第92页：两项内容

The monitoring And controlling of Chemical Process Process intensification

第93页：原位监测的意义

Ifsmallamountofadangerouspollutant(X)willformintheprocessofareactionasaside-product,anditsformationisfacilitatedunderhighpressureandathightemperature,insitumonitoringoftheformationof Xcouldbeappliedto

第94页：过程强化的定义

2. Process intensification

• a strategy for making dramatic reductions in the size of a chemical plant so as to reach a given production objective. Definition:
• via improvement of technical methods
• via improvement of technical methods

第95页：设备改进的方向

2. Process intensification Process intensification via improvement of equipment These reductions can come from shrinking the size of individual pieces of equipment cutting the number of unit operations or apparatus

• Process intensification via improvement of equipment
• Static Mixer Reactor
• Monolithic Catalyst
• Micro reactors

第96页：静态混合反应器

（1）Static-mixer-reactor (SMR)

• The technology of stirring has been greatly intensified during the last 30 years.
• Surprisingly, this was achieved not by improving mechanical mixer but quite the opposite by abandoning them —in favor of static mixer.
• These devices are fine examples of process-intensifying equipment.
• They offer a more size-and energy-efficient method for mixing or contact fluid.

第97页：苏尔寿静态混合反应器

Sulzer S MR static-mixer-reactor,whichhasmixingelementsmadeofheat-transfer tubes,cansuccessfullybeappliedinprocessesinwhichsimultaneousmixingandintensiveheatremovalorsupplyarenecessary,suchasinnitrati

第98页：静态反应器的缺点

Sulzer SMR static-mixer-reactor

• One of the more important disadvantages of static-mixing-reactor is their relatively high sensitivity to clogging by solids. Therefore, their utility for reactions involving slurry catalysts is limited.
• Sulzer solved this problem (at least partially) by developing structured packing that has good static-mixing properties and that simultaneously can be used as the support for catalytic material.

第99页：整体式催化剂

(2). Monolithic catalyst

• Materials used in the preparation of monolithic catalysts:
• Metallic or Non-metallic substrates
• Which could provide a multitude of straight narrow channels of defined uniform cross-sectional shapes.
• To ensure sufficient porosity and enhance the catalytic ally active surface, the inner walls of the monolithic channels are usually covered with a thin layer of wash coat, which acts as the support for the catalytic ally active species.

第100页：整体式催化剂结构

第101页：整体式催化剂的特性

The characteristics of monolithic catalysts

• verylowpressuredropinthesingleandtwophaseflow,onetotwoordersofmagnitudelowerthanthatofconventionalpackedsystems;
• highgeometricalareasperreactorvolume,typically 1.5-4 timesmorethaninthereactorswithparticulatecatalysts;
• high catalytic efficiency,practically 100%duetoveryshortdiffusionpathsinthethinwashcoatlayer;
• exceptionallygoodperformanceinprocessesinwhichselectivityishamperedbymass-transfer.

第102页：微反应器

(3). Micro-reactors

• Micro-reactors are chemical reactors of extremely small dimensions that usually have a sandwich-like structure consisting of a number of slices with micro-machined channels.
• The layers perform various functions, from mixing to catalytic reaction, heat exchange, or separation.

第103页：微反应器的优势

(3). Micro-reactors

• Integration of these various function within a single unit is one of the most important advantages of micro-reactors. The very high heat-transfer rates achievable in micro-reactors allow for operation highly exothermic processes iso thermally, which is particularly important in carry out kinetic studies.
• Very low reaction-volume/surface area ratios make micro-reactors potentially attractive for processes involving toxic or explosive reactants.

第104页：技术方法改进的方向

• Process intensification via improvement of technical methods
• Multifunction rector
• Membrane reactor
• Integration of separation techniques
• Alternative energy sources

第105页：多功能反应器

(1). Multi-functional reactors

• These can be described as reactors that, to enhance the chemical conversion taking place and to achieve a higher degree of integration, combine at least one more function that conventionally would be performed in a separate piece of equipment. For example: Reverse-flow reactor
• To date,reverse-flowreactorshavebeenusedinthreeindustrialprocesses, SO 2 oxidation,totaloxidationofhydrocarbonsinoff-gases,and NOx reduction.

第106页：换热与反应的集成

• Itintegratedthefunctionofheattransferandthatofchemicalreaction.
• For exothermic processes,theperiodicflowreversalinsuchunitsallowsforalmostperfectutilizationoftheheatofreactionbykeepingitwithinthecatalystbedand,afterreversionoftheflowdirection,usingitforpreheatingthecoldreactantgases.

第107页：膜反应器

(2). Membrane reactors

• Membrane reactor is one kind of multiple function reactor integrating the function of chemical reaction and separation.
• It can be used for selective in situ separation of reaction products, thus providing an advantageous equilibrium shift, enhancing the conversion of the reactants and the yield of the target products.
• It also can be applied for controlled distributed feed of some of the reacting species.

第108页：膜反应器的应用现状

(2). Membrane reactors

• The membrane can enable in situ separation of catalyst particles from the reaction products.
• Practically, no large-scale industrial application of membrane reactors have been reported so far. The primary reason for this most definitely is the relatively high price of membrane units, although other factors, such as low permeability, as well as mechanical and thermal fragile ness also play an important role.

第109页：膜蒸馏的优点

The advantages of membrane distillation

• 100%rejection of ions,macro-molecules,colloid,cells and other non-volatiles；
• loweroperatingpressureacrossthemembranethaninthepressuredrivenprocesses；
• less membrane fouling,due to large pore size；
• potentially lower operating temperatures than in conventional evaporation or distillation.

第110页：杂化分离

(3). Hybrid separations

• Many of the developments in this area involve integration of membranes with another separation technique.
• In membrane absorption and stripping, the membrane serves as a permeable barrier between the gas and liquid phases.
• Membrane distillation is the best known hybrid, and is being investigated worldwide. It basically consists of bringing volatile component of a liquid feed stream through a porous membrane as a vapor and condensing it on the other side into a permeate liquid.

第111页：替代形式与来源的能源

(4). The use of alternative forms and sources of energy Several unconventional processing techniques that rely on alternative forms and sources of energy are of importance for process intensification.

第112页：空化与超声的作用

This may have various effects on the reacting species, from homo ly tic bond breakage with free radical formation, fragmentation of polymer chains by the shock wave in the liquid surrounding the collapsing bubble.

• For solid catalyzed systems, the collapsing cavities additionally can affect the catalyst surface----this, for example, can be used for in situ catalyst cleaning/rejuvenation.(4). The use of alternative forms and sources of energy

第113页：太阳能的利用

• Solar energy also may play a role in chemical processing. A novel high temperature reactor in which solar energy is absorbed by a cloud of reacting particles to supply heat directly to the reaction site has been studied.
• Microwave heating can make some organic synthesis proceed up to 1.24 times faster than by conventional techniques.(4). The use of alternative forms and sources of energy

第114页：参考文献

参考文献

第115页：参考文献（一）

• 1. 吴越著。催化化学。北京，科学出版社，19902.高正中编。实用催化。北京，化学工业出版社，19963. Choudhary V. R, Rajput A. M，Pra bha kar, B., None quil in b rium Oxidative Conversion of Methane to CO and H 2 with High S ele cv it y and Productivity over Ni/Al 2 O 3 at Low Temperatures。J. Catal.,1993,139:324~328
• 4. Hickman D. A and. Schm tii dt L. D,。Production of Syn gas by Direct Catalytic Oxidation of Methane。Science, 1993, 259:343~3465.法尔夫 J. 主编。王杰等译。一氧化碳化学。北京，化学工业出版社，19856.唐有祺。展望今后化学之发展。化学通报，1998，7：6~
• 97. Trost Barry M。A biological Catalysis for Synthesis Efficiency.。Pure & Appl. Chem.,1992,64(3):315~322

第116页：参考文献（二）

8. Farr auto R. J.. Heck R. M.,。

Environmental Catalysis into the 21 st Century。

Catalysis Today, 2000,55:179~1879. Hag g in, Joseph。

Catalysis Gains Widening Role in Environmental Protection。

C&EN, 1994,(Fe B,14):22~3010. Anastas Paul T., Bartlett Lauren B., Kirchhoff Marry M., Williamson Tracy C.。

The Role of Catalysis in the Design, Development, and Implementation of Green Chemistry。

Catalysis Today, 2000,55:11~2211. Paul. T. Anastas, Tracy C. Williamson,。

Green Chemistry, Designing Chemistry for the Environment。

American Chemical Society, 199612.黄仲涛、林维明、庞先桑、王乐夫编著。

工业催化剂设计与开发。

华南理工大学出版社，199013.戚蕴石编著。

固体催化剂设计。

华东理工大学出版社，199414.沈师孔，闵恩泽。

烃类晶格氧选择氧化。

化学进展，1998，10（2）：137~145