SULFUR DIOXIDE-ETHANOL-WATER PULPING OF HARDWOODS

The Tennessee Valley Authority (TVA) has developed a two-stage process to separately convert hemicellulose and cellulose to sugars leaving behind a high-lignin solid residue. Research at The University of Alabama has led to a proposed three-stage process utilizing sulfur dioxide to remove hemicellulose, followed by organosolv delignification to remove lignin and the remaining hemicellulose, then acid hydrolysis of the cellulose to glucose. The purpose of the work presented in this paper was to determine whether the sulfonation and delignification steps could be successfully combined. This would result in a simpler process with improved yield of glucose.

Pulping of hardwoods in a sulfur dioxide-ethanol-water system has been shown to give a 50 to 52 percent yield of solid residue with a lignin content of approximately 7%.These results offer improvements to the TVA process in several ways. Removal of the lignin from the lignocellulose matrix would allow more efficient acid hydrolysis of cellulose and the use of less severe conditions. Delignification also serves to increase yields from enzymatic hydrolysis. Use of an organosolv to remove lignin prior to condensation reactions from acid hydrolysis would produce a lignin product which is more reactive and has higher commercial potential. The results of this work have shown the feasibility of combining the University process with the TVA process while maintaining a two-stage process.     

KINETICS OF THE HYDROLYSIS OF ACRYLONITRILE TO ACRYLAMIDE OVER RANEY COPPER

Measurements of the kinetics of the hydrolysis of acrylonitrileover Raney copper catalysts have been made in the temperature range 40 to 100°C in a tubular reactor operated differentially with and without recycle and over concentration ranges of 0-25 weight percent acrylonitrile, 0-35 weight percent acrylamide and 40-99 weight percent water.

For the concentration range 0 to 7 wt. % acrylonitrile and 0 to 7 wt. % acrylamide, data were fitted by an adsorption model of the type

A + K,CA + KCCC and at higher concentrations by the powers law expression

The activation energy for the reaction was found to be 49.2kJmol^-1. Both models showed that the product acrylamide strongly inhibits the reaction.     

IN SITU LEACHING OF URANIUM USING DILUTE SULFURIC ACID AND MOLECULAR OXYGEN

The technical feasibility of in situ uranium leaching using dilute sulfuric acid and molecular oxygen has been assessed and the important process parameters examined by use of laboratory high pressure leaching columns.

The dilute H₂SO₄/O₂ lixiviant was effective in leaching uranium from the ore samples tested. The leaching process was chemical reaction rate limited and can be represented using pseudo first-order kinetics. The leaching rate constant is proportional to the proton concentration of the lixiviant.

Much of the uranium was leached from the ore before decomposition of carbonate minerals by the acid was complete. Acid consumption per pound of U₃O₈ increased sharply as the uranium recovery level exceeded 70%. There appears to be a minimum oxygen pressure for effective uranium leaching. A pressure of 2758 KPa was adequate for the ore samples tested     

DYNAMIC ADSORPTION OF S02 ON ZEOLITE MOLECULAR SIEVES†

Sulfur dioxide is one of the major pollutants resulting from fuel combustion. Numerous dry, semi-dry and wet processes have been developed for pollution control of sulfur dioxide. Solid carbonates, natural and synthetic zeolites, ion exchange resins and carbon based sorbents are the most commonly used dry sorbents for sulfur dioxide removal

In this study, measurements of the adsorption properties of sulfur dioxide on zeolites were investigated. The adsorbents used in this work are 5A, 4A and AW300 type molecular sieve zeolites. Adsorption equilibrium parameters were determined from the pulse chromatographic response to injections of low concentrations of sulfur dioxide. The method of moments were used to evaluate the adsorption equilibrium parameters from pulse chromatographic experiments. Data, such as adsorption equilibrium constants or reaction rate parameters are essential in the design of adsorption systems or reactors in which sulfur dioxide is removed

The experiments were conducted in a temperature range of 523-718 K. The relatively strong adsorption properties of sulfur dioxide on zeolites necessitated the use of high carrier gas flow rates and subsequently non-isobaric operation. Non-isobaric pulse chromatography theory was found to describe accurately the adsorption trends." printpubdate="Adsorption equilibrium constants of S0₂ were found to decrease considerably with increasing temperature. It was also found out that adsorption of SO₂ on the adsorbents investigated were found to decrease in the order of AW300 ≤ 4A ≤ 5A. The adsorption equilibrium parameter of S0₂ on 5A was found as 11.78 at 673 K, whereas it has a value of 157.11 at 523 K. The adsorption equilibrium parameter of S0₂ on 4A zeolite was determined to be 8.63 at 718 K and 213.78 at 523 K.     

INVITED REVIEW ABSORPTION OF NOX GASES

Oxidation of nitric oxide is an important step in NO_x absorption. Recent advances namely catalytic oxidation and the use of slrong oxidizing agents have been reviewed. The refinements which have been made in the kinetics of NO oxidation have been discussed. Several liquid phase absorbents have been suggested for the NO removal, particularly for the purpose of pollution abatement. Different models for NO oxidation using nitric acid have been analysed and the limitations of published information have been brought out.

Absorption of tetravalent nitrogen oxide (NO₂ and N₂O₄) has received considerable attention. The absorbents include water, nitric and sulfuric acids, sodium hydroxide, sodium sulfite and sodium chlorite. Absorption in water and nitric acid is important in the manufacture of nitric acid. The published information on the mechanism of NO₂ and N₂O₄ absorption in water has been critically analysed. The problem of nitrous acid decomposition has been analysed on the basis of film theory. The predictions agree favourably with the available experimental data.

A new mathematical model has been developed for a packed column. Performance charts have been prepared which take into account the effects of concentration of nitric acid, superficial liquid velocity, temperature and the partial pressures of various components. A simplified model on the basis of NO oxidation has also been presented.

Various process design aspects have been discussed in detail. Optimum values for various operating parameters exist and basis for their selection has been explained. Some engineering aspects such as the selection of equipment and material of construction have also been discussed. A comparison between semi-batch and continuous modes of operation has been presented. The problem of the manufacture of pure nitrites has been analysed

Specific recommendations have been made regarding the use of equations and procedures in design. The knowledge gaps have been clearly brought out and suggestions have been made for future work     

Surface Characterization of Vulcanized Rubber Treated with Sulfuric Acid and its Adhesion to Polyurethane Adhesive

Modifications produced on a vulcanized styrene -butadiene rubber surface by treatment with sulfuric acid were studied and several experimental variables were considered.

The treatment of R1 rubber with sulfuric acid produced a noticeable decrease in contact angle which was mainly ascribed to an increase in surface energy due to the formation of sulfonic acid moieties and C=O bonds, and the removal of zinc stearate. The rubber surface swelled and became brittle as a result of the treatment, and when flexed microcracks were created. A rubber surface layer modification was produced with a consequent decrease in tensile strength and elongation-at-break values. The treatment enhanced the T-peel strength of R1 rubber/polyurethane adhesive joints and the locus of failure was cohesive in the rubber.

The optimum immersion time in H₂SO₄ solution was less than 1 min., and the reaction time in air was not found to be critical; the neutralization with ammonium hydroxide and the high concentration of the sulfuric acid (95 wt%) were essential to produce adequate effectiveness of the treatment.     

硫磺流化法还原钛白石膏工艺模拟研究

利用硫磺、碳等还原硫酸法钛白粉生产副产物钛白石膏是处理钛白石膏堆放问题的方法之一。针对硫磺在回转窑分解钛白石膏制硫酸和氧化钙的过程存在时间长、硫磺用量大、硫化钙产量不高等问题,提出了以钛白石膏为原料利用酸浸法去除铁杂质后,利用硫磺为还原剂将石膏在气固竖式反应器中煅烧生成硫化钙和二氧化硫,前者再与硫酸钙煅烧制得氧化钙和二氧化硫,得到的氧化钙可以中和废酸和废水,产生的二氧化硫用来制硫酸的方法。先利用反应热力学计算软件HSC分析确定实验方案,分别在流态化实验（800 ℃,保温40 min）和煅烧实验（1 100℃,保温1.5 h）后得到硫化钙转化率与氧化钙纯度均达到90%左右。再利用Aspen软件模拟了工艺流程,模拟出二氧化硫体积分数可达12.09%,满足制硫酸的需求。硫酸生产成本估算为263.9元/t,具有较大的市场前景。     

硫磺分解氟石膏制高纯氧化钙联产硫酸的研究

氟石膏是氢氟酸生产过程中的副产品,为了变废为宝,利用硫磺为还原剂,采用两段法分解氟石膏制备硫酸和高纯氧化钙。一段反应为硫磺气化后氧化氟石膏生成硫化钙与二氧化硫,二段反应为一段反应生成的硫化钙与氟石膏高温反应生成氧化钙与二氧化硫,生成的氧化钙可用来中和废酸,也可进一步纯化后售卖,二氧化硫可用来制酸。此方法不但能实现硫、钙资源在厂区的内循环,而且能降低硫酸成本。通过热力学分析和一、二段不同反应温度及二段不同原料配比验证得到最佳反应条件为：一段反应温度为800 ℃、保温2 h;二段反应温度为1 100 ℃、保温1.5 h,反应物硫化钙与硫酸钙物质的量比为1.2:3。一段反应得到的硫化钙质量分数为83.51%,二段反应得到的氧化钙纯度为85.38%,并可进一步提纯到99.87%。硫酸生产成本估算为117.9元/t,远低于硫酸市场价格,具有较大的市场前景。     

ON THE PERMEATION OF SOME GASES THROUGH THE LAMELLAE OF STATIC FOAMS. A PRELIMINARY APPROACH

Basing on the capillary method for the determination of foam bubble size, a method was proposed for establishing values of permeability coefficients of several gases. The permeability coefficients of He, Ar, H₂, N₂, CH₄ through the lamellae of static foam bubbles were preliminarily determined using this method.

A rough dependence of the N₂ permeability coefficient through the lamellae of static foam bubbles on the foam wetness and surfactant concentration was also found.

The results obtained lead to the conclusion that the Princen-Mason diffusion model of gas permeation through an isolated soap film was inadequate in the case of permeation through lamellae of bubbles forming a static foam.

A hypothesis that the gas permeation through the lamellae of a static foam is primarily caused by liquid convection in the lamellae core was put forward.     

AMMONIA CATALYZED ORGANOSOLV DELIGNIFICATION OF POPLAR

A parametric investigation of NH₄OH catalyzed solvent delignification of poplar was conducted to define pretreatment conditions which would yield an optimal separation of the biomass components and an enzymatic susceptible solid carbohydrate phase. Delignification parameters of interest included concentration of NH₄OH, time and temperature of the reaction, and type of solvent. The addition of 0.82 M NH₄OH to the delignification liquor increased lignin removal and decreased carbohydrate degradation, but increasing NH₄OH concentration had no additional effect. At lower reaction temperatures, the extent of delignification increased with reaction time; at higher temperatures, a “relignification” of the pretreated wood was observed. The delignification and hemicellulose solubilization were modelled and rate constants reported. No major difference between three potential pulping solvents—ethanol, butanol, phenol—was observed. The enzymatic susceptibility of pretreated wood samples was approximately 6-fold greater than that of the untreated poplar. UV absorbance was used to qualitatively characterize the soiubilized lignins.     

Ferric Oxalate with Nitric Acid as a Conditioner in an Adhesive Bonding System

Stron adhesive bonding of composite resins to dentin and enamel is obtained by conditioning the surface and applying adhesion-promoting compounds. This study examines tensile adhesive bond strengths and effects of the conditioners having various concentrations of ferric oxalate (FO) and nitric acid.

In the first part of this study, the average tensile bond strengths increased with concentrations of commercial FO as received up to about 6.8% and averaged no higher with higher concentrations. After this part of the testing had been completed, it was discovered that the FO as received contained a small amount of nitric acid. Use of solutions having from 6.8% to 20% ferric oxalate as received yielded bonds with strengths that averaged about 13 MPa psi) to dentin and 16 MPa (2,400 psi) to enamel.

In the second part of this study, the FO was stripped of the fortuitous nitric acid and, based on results from the first part of this study, solutions were made up to contain a fixed concentration of purified FO [6.8% Fe₂(C₂O₄)₃] and various known concentrations of nitric acid. The highest bond strengths to dentin and enamel were obtained with the purified FO solution which contained approximately 2.5% nitric acid.     

Evaluation of Different Sulfur-Free Delignification Methods for Hot-Water Extracted Hardwood

Abstract

Hot-water extraction (HWE) of hardwoods may be performed as a part of sequential disintegration of hardwoods in a biorefinery system. In this study, different sulfur-free delignification methods were investigated for their respective effectiveness in lignin removal from unextracted (SM) and hot-water-extracted sugar maple (SMHWE). Peracetic acid and tetrahydrofurfural alcohol were investigated as attractive delignification agents, which may be produced on site (biorefinery products). Oxygen was used in combination with the organic solvents acetone and ethanol, designed sugar fermentation products from hydrolyzed hot-water extracts.

The delignification degree and delignification selectivity were compared for SM and SMHWE. SMHWE consistently showed a higher degree of delignification. Also, a higher selectivity was observed in delignification of SMHWE with all investigated agents except peracetic acid. Oxygen delignification in an acetone:water mixture was the most selective in delignification of SMHWE. The delignification results obtained using the acetone-water-oxygen system for sugar maple were confirmed using Eucalyptus (unextracted, Eu, and hot-water-extracted, EuHWE). These results indicate that the structural and chemical changes occurring during HWE of hardwoods provide for a more efficient subsequent delignification with a wide range of delignification agents.     

连续酸解在硫酸法钛白生产中的应用

硫酸法钛白生产会产生大量的废水、废酸和废气,给环境造成严重的污染。通过分析硫酸法钛白生产酸解的原理,对比连续酸解与间歇酸解主反应时产生的废气排放对比,续酸解与间歇酸解的经济对比,体现连续性酸解尾气处理的优越性。     

过氧甲酸预处理对甘蔗渣酶解和发酵的影响

以甘蔗渣(SCB)为原料,经过氧甲酸(PAP)预处理后加入酶进行水解,并以水解液发酵产乙醇,考察预处理时过氧化氢(HPP)浓度变化对甘蔗渣酶解和乙醇得率的影响。实验结果表明：在甘蔗渣PAP预处理过程中,HPP与甲酸(FAP)体积比为1∶1时,预处理甘蔗渣(PAP-SCB-1)的木质素脱除率达84.30%;在纤维素酶用量为10 FPIU/g(以预处理后的甘蔗渣质量计)时,PAP-SCB-1水解72 h葡萄糖得率为98.71%,较单独过氧化氢预处理甘蔗渣(HPP-SCB,葡萄糖得率9.11%)和单独甲酸预处理甘蔗渣(FAP-SCB,葡萄糖得率7.06%),分别提高了9.84和12.98倍;PAP-SCB-1水解液经24 h发酵后,乙醇得率为84.06%,比HPP-SCB(76.20%)和FAP-SCB(75.15%)均有增加。对预处理前后物料的化学成分变化、比表面积和结晶度进行测定,结果显示：经PAP预处理后可以显著脱除甘蔗渣中的木质素,木质素的量由未经预处理的21.27%降低到10%以下;比表面积和结晶度都有提高,PAP-SCB-1的比表面积和结晶度分别为13.01 m²     

ACETIC ACID AS AN OXYGEN CARRIER BETWEEN TWO PHASES FOR EPOXIDATION OF OLEIC ACID

Acetic acid was found to be an effective oxygen carrier for epoxidation of oleic acid. The reaction model of oleic acid epoxidation in the two-phase reaction system was systematically analyzed and the rate determining step was experimentally identified.

The results indicated that the rate of oxidation of the unsaturated acid was independent of the concentration of oleic acid and depended on the mixing rate and the rate of formation peracetic acid which in turn depended on the concentration of acetic acid, strength of acid catalyst and the oxygen source, hydrogen peroxide. In the region of reaction control, the rate equation of epoxidation was found to be

$

where k = 2.98 × 10^-2 M^-2 min^-1 at temperature of 35^°C.     

A MONTE-CARLO APPROACH TO THE INTERPRETATION OF BUBBLE PROBE SIGNALS IN FREELY BUBBLING FLUID BEDS†

The interpretation of the signals generated by a double probe may be done by the three characteristic times method:

t₁ the time duration of the pulses;

t₂ the time shift between the signals of the two probes;

t₃ the time interval between two pulses on one channel.

Each of these times is largely dispersed and the corresponding histograms may be constructed.

The present work is a trial to go over from the time histograms to physical properties of the bubbles combining a Monte-Carlo simulation and a flexible simplex optimisation procedure.

As a result, the percentage of oblique bubbles cutting just one level, the bubble size distribution, the average velocity-size relation, and the individual dispersion around it may be defined.

The procedure is finally applied to experimental results obtained with a light probe in a fluid bed of glass beads.     

ABSORPTION AND DESORPTION TO AND FROM LIQUID FILMS ON INCLINED PLANES

Two published theoretical models are examined and applied to experimental results for absorption and desorption. The system used was CO₂/H₂O and studies were made for liquid film flow down inclined planes. Experimental results give “Reduced” values of mass ransfer rates.

Interferometric studies give interfacial concentration, penetration and film depths, and take-up of carbon dioxide. In the case of desorption the interferograms are distorted by “deflections.”

All the experimental values for absorption and desorption differ from those calculated from theoretical models.

Desorption is not a mirror image of absorption, and it is approximately 75% of the transfer rate of absorption over a wide operating range.

A comparison is made of the behaviour of static pools and flowing liquid films.     

EVALUATION OF CONDUCTIVE HEAT TRANSFER MECHANISMS BETWEEN AN IMMERSED SURFACE AND THE ADJACENT LAYER OF PARTICLES IN BUBBLING FLUIDIZED BEDS

The evaluation of the heat transfer coefficient h_wp between a heat exchanging surface immersed in a gas fluidized bed and the adjacent layer of dense phase particles is analyzed in this contribution. Gas convective and radiant effects are not included in the present analysis.

The inclusion of h_wp, or an equivalent formation, in mechanistic models describing heat transfer has been necessary because the sudden voidage variation close to the immersed wall restrains significantly the heat transfer rate. However, there is not at present a widely accepted expression to evaluate h_wp.

A precise formulation for h_wp accounting for transient conduction inside spherical particles, the Smoluchowski effect, the concentration of particles in the adjacent layer (N_p) and an effective separation gap (l₀) is developed here.

Although N_p can be estimated, in principle, from experimental evidence in packed beds, and it is reasonably expected that l₀ = 0, the analysis of experimental heat transfer rates in moving beds, packed beds, and bubbling fluidized beds indicate that values of h_wp are, in general, smaller than expected from these assumptions. Appropriate values of l₀ and N_p are then stimated by fitting the experimental data.

The probable effect of surface asperities is also discussed by analyzing a simplified geometrical model. It is concluded that the parameter l₀ can be also effective to account for particle roughness, independently of thermal properties.     

The simultaneous activation of methane and carbon dioxide to C2 hydrocarbons under pulse corona plasma over La2O3/γ-Al2O3 catalyst

The pulse corona plasma has been used as an activation method for reaction of methane and carbon dioxide, the product was C₂ hydrocarbons and by-products were CO and H₂. Methane conversion and the yield of C₂ hydrocarbons were affected by the carbon dioxide concentration in the feed. The conversion of methane increased with increasing carbon dioxide concentration in the feed whereas the yield of C₂ hydrocarbons decreased. The synergism of La₂O₃/γ-Al₂O₃ and plasma gave methane conversion of 24.9% and C₂ hydrocarbons yield of 18.1% were obtained at the power input of plasma was 30 W. The distribution of C₂ hydrocarbons changed by using Pd-La₂O₃/γ-Al₂O₃ catalyst, the major C₂ product was ethylene.     

秸秆中木质素对其超低酸水解过程的影响

以湖北稻草秸秆为研究对象,研究了超低酸水解木质纤维素的适宜条件,测定了适宜条件下的超低酸法水解15种不同种类秸秆的纤维素及半纤维素的转化率、还原糖得率及结晶度的变化。实验结果表明:秸秆投料量3 g、硫酸投料量45 mL(硫酸质量分数0.05%)、搅拌转速500 r/min、反应温度210 ℃、反应时间10 min为适宜的水解条件。对15种不同种类秸秆的水解结果统计得到,随着秸秆中木质素含量的增大,纤维素和半纤维素的转化率都逐渐降低,还原糖得率逐渐降低;通过SEM和X衍射分析水解前后的木质纤维素结构,得到了木质素影响水解过程的方式:1)木质素含量越大,纤维素的结晶度越大,纤维素的非晶化越困难,从而影响了纤维素的水解;2)原木质素不溶于反应体系且在酸性条件下相对稳定,富木质素层的木质素阻碍反应物与产物扩散,使富木质素层内的纤维素、半纤维素水解速率降低;3)木质素含量越高,木质纤维素的富木质素层越厚、强度越大,水解时难以从颗粒表面脱落,进一步降低水解速率。