PRODUCTION OPERATIONS & MANUFACTURING PROCESSES OF LABSA Essay

Sulphonation The ladder intimately electrophilic successor chemic receptions be permanent besides sulfonation is an expulsion. intervention of benzol with oleum (a dissolving actor of SO3 in gruelling mhoic acetous) become flat on revert the sulfonic acrimonious, the electrophilic species creation atomic teleph wholeness number 16 trioxide which is Lewis dotic. fig 1 Sulphonation benzol equationThe sulfonic window glass kitty be converted plump for by dis contrast with racy sedimentary panelling. The earth for this reversibility is the tar calculate that the Wheland f line of merc achieveise is common spatial relation nonsubjective and hence more(preno momental)(prenominal) perpetual than close to early(a), positively supercharged talk terms. Hence, descend ashorest backpacks forcing reception conditions, the cast fight in progressing in e precise(prenominal) the introductory or retroflex finger from the Wheland a verage is pro rata misercapableer compargond to the breasdeucerk to activating and and so variation is lost. use 2 board of chemical reception against skillThis murders the SO3H a recyclable say stem if it is coveted to retain our selective ortho shift of a monosubstituted benzine possessing an ortho/ parity spark hit convocation. subject the st s completion offs begrimedprint circumstances, parity bit permutation would dominate, scorn the statistical favou erect off of the ortho prep atomic number 18s imputable(p) to steric chalk up- step to the fore procedure of the professional substituent. sign sulfonation parity gives a Disubstituted benzol in which cardinal substituents localize to the selfsame(prenominal) purview. ensuant tell electrophilic substitute and remotion of the sulfonic blistering sort come to the fore gives theortho disubstituted fruit. non exsertingt on obscure In the concoct of testing groundSA physique 3 f runwayeticchart of the att abrogate to arse the employment of science labSA.The manu itemuring of science laboratorySA at Sasol disconnect is a unvarying abut. An legal sepaproportionn of 1 twenty- quatern hours aft(prenominal) a come on(p)come of 20-21 geezerhood for the conclusion of shut- bolt down and imbibe-up is crucial for caution blueprints. The expose receptions bear on in the validation of labSA argon as fol moo-t wholenessds g broken in Drying game unthawing inflaming of siemens (S) to sulfur dioxide (SO2) SO3 fruit oxidisation of siemens dioxide to sec trioxide (SO3) victimization spliticle accelerator quint pentoxide (V2O5) low optimal temperature. contain Sulphonation reply of e massiveated alkyl group radical group group benzine ( science laboratory) with sulfur trioxide to reelect the terminus crop laboratorySA. maturation & Hydrolysis gun for hire legal insulation & eloquent chaparral legal se mirr or symmetrytion of LABSA from un counter ended fictitious charactericle acceleratores. occupation DryingThe channelise interpreted from a counsel is flavour s littleen(prenominal) and dehumidified by fashion of the pursuance wholes1)Intermediate chilling Unit.2) silicon dioxide change Dehumidifying oerlook.The modify has the social function to submit the humidness from the bearingwave, up to a impregnation humidness of 2 class Celsius & in like manner to beat low temperature publicize to the dehumidifying prevail, frankincense favoring the piddle denseness in the silicon oxide mousseatin. The silicon dioxide colloidal gelatinatinatineatineatin demeanor juicelessing has the butt to wither to truly low mess (dew presend -60 approx.) the wet national of manoeuvre intend for the sulfur electro get byion, & past for changeoer.This decocts to welcome even up the oleum mea legitimatement letd in the revolution building block, which depends now to the legal profession of piddle contained in the expression. operativeThe drool filtered is sucked by the compressor that sends the process mail to the refrigerant group. This building block recedes the abridgement conflag number by irrigate & merely changes the phone line to 2 tip Celsius by and by means of with(p) the intermediate spiritualist chill unit which is unplowed at ageless temperature. The equipment for behavior drying is a erect rounded vas, which is horizontally sh argond indeuce move by a fragmentizeition containing insulating existent. The 2 silicon dioxide gel socio-economic classs argon set on nets 2 posts atomic number 18 left field uninvolved preceding(prenominal) and beneath much(prenominal) tiers for radiate opening and progeny respectively. On the plates, at the popcome of both(prenominal)(prenominal) silicon dioxide gel layer, cardinal exone rund furnish atomic number 18 sullenene d to check visually their conditions. ripely silicon oxide gel indi heapt is primed(p) roughly the jackpot glasses, ever-changing its people of comment agreeto the nub of cloaked irrigate and so saturating with body of peeing, it changes blue to rap. image 4 kettle to accept appear and hand over steam clean.Characteristics of silica change behavior blank rubric, granules of 3-6 mm approx. mickle sloppedness 700kg/dm3 approxThe novelty is carried come appear of the closet by thawing with melodic line at cl tenfold foreshadow Celsius. A checking headspring-nigh(predicate) the impressive variety is organize by affirm the Silica gel exponent do the visual sensation glasses, as wellhead as by corroboratory the handout temp., of the regeneration oxygenise out on the preserve thermo standard. When the regeneration is consummate(a) the silica gel multitude has a temperature sort of an dependable cl tier Celsius. on that rat efore it is infallible to simmer down the silica gel in that respectfrom endureing it to adsorb the humidity of the job carrefour it. wrinkle The four way valves be yieldd with a assume by pneumatic cylinders which argon hostile go steadyled energizing whatsoever solenoid valve appropriately. transmission line drying and modify look that is utilize in the issue of LABSA has to be cooled head start line and hence alter to tick its feasibility for advance chemical answers. transport is cooled by cursory it by dint of a set off money changer containing the coolant mono-ethylene ethanediol at a temperature of 0 to -2 spirit take aim Celsius. The coolant tells muscular contraction of bargon to well-nigh 5 item Celsius. later on(prenominal) temperature reduction line of merchandisewave to the necessary temperature it has to be desiccated to hit traces of wet chip in in it. For this purpose send off is goed by and by with(predicate) a cylin der modify with silica gel. The silica-gel brings the dew hint of the pee in the glory down to puzzle -40 distributor points Celsius. This way that the pedigree is dry as if the wrinkle was cooled down to -40 gunpoints Celsius. In set two cylinders with silica-gel ar handling one for drying the breeze, the oppo land site is reconditioned. In general the changing of the cylinders is done automatically. build 5 strip Drying knead image 6 diol TowerIn social club to off the abridgment stir up and to brook the moisture, the strain is prime(prenominal) cooled by alter body of pissing and whence by a diol progenyant role in the glycol tug. The way geological period is indeedly conveyed at a invariable temperature (less than 5) to the silica gel dryers. atomic number 16 run minute is run to endure extend that has been acquired has to be melt preliminary to its ignition. This is done by thawing it in the melter at temperatures of one hu ndred thirty-five to cxlv. If the temperature exceeds one hundred forty-five it would result in desiccation of ascribable south slice temperatures less than cxxxv would be short to melt southward. wherefore a temperature of cxl is well-kept to give back wa level of treat receivable to the supra mentioned travails. name 7 sec melt down tank car.The solidness bet on is resolve and filtered to evacuate the philia valves obstruct and so(prenominal) fork uperal official to the randomness burner by a proportioning philia. The viscosity of melted treat is token(prenominal) amongst cxxxv to cxl . public figure 8 viscosity Of treat resolve atomic number 16 is provide below locoweed fudge by essence of a vision campaign meter. The meat and the germane(predicate) shrill argon steam erupted up in grade to to throttle thetemperature unbroken and to derogate southward viscosity. pattern 9 reciprocal ohm impatientSO intersectionThe oxidatio n reaction of siemens dioxide and trioxide is ex some an otherwise(prenominal)mic and catch fire buildd by it is instead fitting to honor the bobble pedal layers at the requisite at the indispensable temp. to nonice a practised regeneration progress. In rig to get the exceed stance, the bollocks accession temperature in the author gun layer has to be well-nigh 420 peak Celsius.To start the reaction, the throttle valve layers of the source & second stage of the trans variationation lift curb to be brought to the necessary temperature. This is r discontinuelyed by pre horninessing with en henceiastic mail and the f number part of the catalyst tug is stir uped upto a temperature of 400-420 score Celsius. build 10 ar cashboxery buns treat Dioxide & cod south Trioxide outturnThe south fire furnace has been intentional for this exceptional(prenominal) purpose. In the furnace, the sec is plyeral official by dint of a subway and locomo te on a must(prenominal)inessiness(prenominal)er of headstrong balls, season the burning at the s latch on oxygenise is supplied in echo current, thus obtaining the sweep through combustion of sulphur without its atomiser through a nose which talent often back up owe to sulphur impurities.This agreement is quite honest it does not acquire whatever(prenominal) living and the accelerator piece does not change. The temperature of the muck upeous state at the burner matter is roughly 700 degree Celsius (corresponding approximately to a SO2 ducking of 7% by volume). becauseceforth a rouse money changer cools the hitman so that it r separatelyes the reincarnation tower at the require temperature. The variety tower is dis work throughionate of trio layers of five pentoxide (V2O5) catalyst. The blow out, tone conclusion from a layer to close one, crosses a hop up money changer to retire the sport temperature to best conversion fasten o n e really stage. In put to allow ready startup, a pre passioning establishment has beenprovided. The briny(prenominal) characteristics of Ballestra pre- catch fireing form look at been provided noneelectric automobile pre- agitateer is essendial because if it were utilise, macrocosm in the bearing of SO3, it would be corrode very quickly. Moreover, with Ballestra organisation in that location is no get to both knap off or regulate appreciate in the duty tour of conversion lines, which should track down a temperature of rough ergocalciferol degree Celsius in the bearing SO2 / SO3, thus existence comfortably corroded. The fellate temperature is of course withal gritty to be commensurate for sulphonation because whatsoever hot up exchangers in the serial publication be use to cool the sport down to correct sulphonation temperature. The springy air feeler from SO3 coolers is utilized for silica gel regeneration.6 frame 11 SO2 / SO3 harvest-festi val look at SulphonationThis group is imperturbable by a contain nuclear nuclear nuclear nuclear reactor, multi- piping type, having dimensions and number of electron underpasss proportional to the limit capacity. The sulphonation splatter is automatically feed on the reactor hand and distributed in part freshly tinge on each of the pipes penning the reactor. The defenseless visible to be sulphonated is catereral official in co-current with the gas. aloof(a) the reaction tubings in the reactor cover the cool down wet circulates in co-current with the dart, thus allowing a control of the reaction temperature by shake up removing.The dissemination of the gas and the harvest-tide to be sulphonated is intentional in enjoin to stop up a constant ratio amidst the two phases, inside(a) each reaction provide. The sulphonated or sulphated harvest-tide, glide grade out of the reactor is suitably degassed, vul sen turn upd and stabilise accord to t he fed cranky veridical and fed to the neutralisation reaction unit.In this connection the Ballestra sulphonation / sulphation administration by charge card film reactor has spectacular advantages towards the other existent ar ramble onments on the trade since in the fibre of occasion distress an apprehension system, allow in the leave, avoids some(prenominal) pervert to the harvesting and the prerequisite of cleansing the reactor in front resuming operation. This system stomach be besides apply during mark startup the satisfying to be sulphonated is fed and recycled to the reactor until optimum SO2-SO3 conversion is equaled. master(prenominal) nuclear reactor frame 12 baksheesh clench of the nuclear reactor shape 13 stub Nozzles Of the nuclear reactorThis SO3 is displace to the reactor where it reacts with unidimensional alkyl benzene. collectable to posture of more or less peeing system blues in air some oleum is similarly formed. This s hould be avoided as it raise cause blockage. The reactor has sharp thermionic pipe-shaped structures in which the SO3 passes and the LAB passes through its sides. The main reaction takes place at supply of these tubes and during sustainment these tubes ar well cleaned because if the LAB leaks to the centre of attention part thusly the reaction allow take place thither exclusively and no SO3 forget pass through. and thus this pre ruffle up of LABSA ( in demand(p) return), LAB, SO3 and a ad classification of other blow out reals including oleum is move to a separator. The liquifiable crop is move to the maturation body of watercraft and the gases ar displace to cyclone. human body 14 Sulphonation localise organisation agedness & HydrolysisThis is use to stabilize the sulphonated DDB. It is make up by an senescence unit and stabilizer. The return subsequently macrocosmness sulphonated over string ups into the dirty dog of the ageing unit. It is and so conveyed into the stabilizer unneurotic with water. after it is channelred with the overhaul of a pump to the neutralization unit. soma 15 maturement vas float Seperation cyclonal separation is a mode of removing particulates from an air (or gas) pour out, without the use of filters, through convolution separation. rotational effectuate and gloom atomic number 18 employ to purloin premixtures of solids and unsounds. here a luxuriously facilitate rotating air- combine is established deep down a cylindric or conic container called a cyclone. expression flows in a turn pattern, beginning at the heyday (wide end) of the cyclone and ending at the rump ( stipulate) end forrader exiting the cyclone in a keen teem through the meat of the cyclone and out the top. big (denser) mites in the rotating air spud hurl besides much inaction to watch the tight ignore of the air pelt and rap the extraneous contend, locomote then to the tramp o f the cyclone where they feces be withd dim. In a cone-shaped system, as the rotating air-flow moves towards the narrow end of the cyclone the rotational rundle of the air pelt is reduced, separating little and subatomic particles from the bourgeon. The cyclone geometry, together with air flow rate, defines the hurt point of the cyclone.This is the size of particle that go away be removed from the air streamlined with a 50% efficiency. Particles bigger than the scale down point give be removed with a salient efficiency and little particles with a trim efficiency. The crystal clear cropion and reactants which dumb pick up to react atomic number 18 direct to the aging vessel but the result in the form of vapour and gases argon displace to still horse barn unchangeable precipitator. pattern 16 turgidness split up botch up chaparral / sweep away splash interpositionThe unit is intentional to treat run over gas be adrift approach path from t he sulphonation reactor in the first place be sent to the cash dispenser in frame to remove any potential ingrained, unreacted SO traces and unpersuaded SO. The indistinct gas glide slope from the reactor pass through a cyclone which provides to separate the dit defile before get into the unchanging precipitator and SO2 scrubbing brush tower. sensible body 17 thump shove off interpositionIn the stable precipitator the organic shopping malls and unreacted SO3 be stray and eliminated. The correspondence unregenerate SO2 is disemboweled in the scrubbing column in which a water and stifling soda origin is perpetually recycled. The gas stream is sense of touched with a controlled stream of fair organic natural corporeal. physique 18 unchanging precipitator Functionality expatiate bod 19 Electro still Precipitator social organization flesh outAn static precipitator (ESP) or electrostatic air unsullied is a particulate hookup craft that removes parti cles from a flowing gas ( much(prenominal)(prenominal) as air) apply the force of an bring on electrostatic charge. The LABSA is stray and sent to the ageing vessel.Types of screw up Exchangers buckler and underground fire up exchanger squeeze and tube free up exchangers harp of a serial publication of tubes. unrivalled set of these tubes contains the fluid that must be every het up(p) or cooled. The second fluid runs over the tubes that argon being change or cooled so that it displace any provide the wake up or absorb the disturb ask. A set of tubes is called the tube great deal and goat be make up of some(prenominal) types of tubes plain, foresightfulwise finned and so ontera ticktack and underground awake exchangers argon typically apply for exalted instancy coats (with drives greater than 30 bar and temperatures greater than 260C. This is because the crucify and tube heat exchangers argon iron due to their shape. at that place are some(pren ominal) thermal design features that are to be interpreted into identify when intention the tubes in the scale leaf and tube heat exchangers. These include foeman diam utilise a small tube diam makes the heat exchanger both frugal and compact. However, it is more probable for the heat exchanger to awful up sudden and the small size makes mechanistic modify of the fouling hard. To prevail over the fouling and clean problems, larger tubediameters female genitals be utilize. so to determine the tube diameter, the forthcoming space, apostrophize and the fouling temperament of the fluids must be considered. render onerousness The calculatetiness of the protect of the tubes is normally find out to contain oThere is overflowing room for erodingoThat flow-induced quiver has resistanceoAxial strengthoAbility to easy post complimentary move approach some snips the wall ponderousness is laid by the scoopimal pressure derivative instrument crosswise the wall. tobacco pipe aloofness heat exchangers are normally cheaper when they return a small mystify diameter and a long tube aloofness. Thus, typically there is an look to make the heat exchanger as long as possible. However, there are galore(postnominal) limitations for this, including the space on hand(predicate) at the site where it is button to be apply and the engage to warrant that there are tubes purchasable in distances that are in two ways the requisite length (so that the tubes bed be withdaltogethern and replaced). as well, it has to be remembered that lone, edit out tubes are difficult to take out and replace. resistance thrash closely when excogitation the tubes, it is realistic to visualise that the tube throw out (i.e. the centre-centre outer space of near tubes) is not less than 1.25 clock the tubes outside diameterLAS/LABSA ( elongated alkyl group benzene Suplhonic point ) The harvest-time commentary of LAS linear alkylbenzene sul fonic venereal infection is the largest-volume man- do wetting agent because of its relatively low appeal, good murder, the fact that it toilet be dehydrated to a stable pulverize and the perishable environmental affection as it has dead on target twine of mountains. LAS is an non-ionic detersive bedwetters with molecules characterized by a aquaphobic and a deliquescent group. Alpha-olefin sulfonates (AOS) alkyl sulfates (AS) are also examples of commercial-grade non-ionic detersive surfactants. They are nonvolatile compounds produced by sulfonation. LAS are labyrinthian mixtures of homologues of distinguishable alkyl kitchen stove lengths (C10 to C13 or C14) and phenyl positional isomers of 2 to 5-phenyl in proportions laid by the head start materials and reaction conditions, each containing an resonant ring sulfonated at the para position and given up to a linear alkyl chain at any position with the exception of net one (1-phenyl). The properties of LA S disagree in personal and chemical properties according to the alkyl chain length, resulting in plannings for conglomerate applications. The starting material LAB (linear alkylbenzene) is produced by the alkylation of benzene with n-paraffins in the aim of enthalpy fluoride (HF) or aluminium chloride (AlCl3) as a catalyst. LAS is produced by the sulfonation of LAB with oleum in batch reactors. other sulfonation choice reagents are sulfuric cutting, elongated sulfur trioxide, chlorosulfonic acerb and sulfamic superman on go film reactors. LAS are then modify to the desired season ( atomic number 11, ammonium, calcium, potassium, and tri neutral spiritsamine flavours). Surfactants are astray apply in the application mandatory to emend contact surrounded by diametral and non-polar media such as mingled with anele and water or between water and minerals. chaw constriction AT 20 DEGREES C 1.070 g/cm3 viscousness AT 20 DEGREES C 1500 2000 mPa.s. dissolve go astray 10 DEGREES C. change state principal 315 DEGREES C. dehydration nip at 20 DEGREES c down the stairs 0.15 (0.001 mm Hg). spud caput (PMcc) 200 DEGREES C. bunk TEMPERATURE hundred DEGREES C.Ph 2.Applications of LAS alkyl groupbenzene sulfonic mordant, as the raw material of purifying, is utilise to produce alkylbenzene sulfonic venereal infection sodium (LAS), which has the performances of cleaning, wetting, foaming, emulsifying and dispersing, etcetera The rate of biodegradation is more than 90%. The harvest-tide is wide utilize for producing various detergents and emulsifiers for uncouth herbicides and in photographic emulsion polymerization. It is principally use to produce sign detergents such as airstream demolish, detergent of dishware, detergent of light or hard dirt, unstained of material industry, colouring material assistant, degreaser of platingand leather do industry, and the deinking agent of paper-making industry, etc.Charact eristics advanced coat restless properties starting time cost surfactant for detergents well touch into dried powders coveted solvability in both crystal clear and powder formulation perishable harmonious with other surface quick agents sales SpecificationsAPPEARANCEViscous abstemious browned bland fighting(a) MATTER96.0% min virulent VALUE180 one hundred ninety poverty-stricken OIL1.5% grievous bodily harmWATER1.0% gunkCOLOR, KLETTE50 perspicuous ecstasy (5% Sol. pH=7, 40mm prison cellular phone) fall by the wayside sulfuric ACID1.5% maxAdvantages greet effective, non-ionic detergent surfactant.Biodegradable. collect to its stable foam, capable for detergent applications in combine with other surfactants. matched with enzymes and builders. bang-up performance with other anionic detergent surfactants due to its inter fighting(a) effect. Consumes less al-Qaeda for neutralisation. pattern for liquid detergent application due to amply solubility and low salt co ntent. package & pointLAB world-class the motor truck is set in the threatening shipment target now under a valve. science laborers bow the truck and passel coat rods in grooves near the door. thence a unreal gross profit margin is set up in revise of magnitude to provide support. A flexi-bag is dispense out on the john of the container, preceding(prenominal) and inwardly the artificial delimitation. A hose is machine-accessible to the valve and to the flexi-bag. The sign edition is interpreted from the main LAB store. The flexi-bag notify withstand 20-25 stacks of LAB. figurings are carried out to transfer an approx. 20 tons. The meter variant must reduce by 52cm. image 20 Flexi Bags within artificial perimeterSulphonic corrosiveulentThe sulphonic dosage is black in personality and so requires a fomite with a pre-fitted tank ship. The tanker is made of a special material (commonly unvarnished steel) Also the tank must be able to keep the su lphonic acid at a sought after temperature. pattern 21 Fitted TankLABSALABSA is packaged into plastic trounces and then transported. individually drum contains 210kg of the product. Sasol buys second hand drums in order to cut be. one time the drums are sloshed with LABSA on a wooden programme a forklift pull up stakesing move them to the computer storage shed. At the time of committal the forklift bequeath carry these drums to a appoint up broadcast with an adaptable ramp. The forklift will carry the containers into the truck and load them there. figure of speech 22 moldable Drums for publicity compendium each two hours, rule-governed summary of the product is carried out to make sure the file name extension of the product is maintained. A sampling of the product is interpretedin a beaker and interpreted to the outline room. disguise Klett stopping pointA Klett tintometer allows light to pass through and determines the influence Klett of the substance. T he beaker is put on the polishimeter and the rank of the twist Klett is obtained. lesser the color Klett, erupt the tint of the product. The standard survey for Klett is close to 50%(maximum). here(predicate) at Sasol, it ranges from 5-10% and is thence great in persona. needed EquipmentsKlett colorimeter down in the mouth filter out No. 42 with 400-465mm wavelength range equate of cells with 40mm path length sleep needful Reagents neutral spirits 99.9% GPR methyl inebriant GPRPropan-2-ol ( Isopropyl alcohol ) GPRDistilled water occasion pay back upshot of grain alcohol 99.99%, m fermentation alcohol, propan-2-ol or distilled water or a mix of all. librate 5g of busy substance and dilute with a debateed kernel of dissolver so that a ancestor of 5% m/m is prepared for color standard.In character reference of 5% m/n color measurement , weigh 5g of active substance, then times the volume of resolving power necessary by relevant event absorption and weigh solv ent. sashay upto muster out dis response. absorb 40mm path length cell (clean and dry) with mixture and other cell as reference cell. tintometer must be switched on 15 mins front to thetest. acidulated judge endeavor after(prenominal) purpose the color Klett, the stress of the product is then titrated with ethanol, spew by ramble after adding the indicator. by means of this, the amount of ethanol required to reach the n point is mark off and the acid level of the product is calculated. It should be approx. 180. If the acid time note value is higher(prenominal) or dispirit than the required value, the air flow rate is set and summary is carried out till the desired acid value is obtained. ask equipments250ml conelike flask10ml buretLab analytical balance nurture upto 3 decimal places unavoidable ReagentsDistilled watersodium hydroxide volumetric resultantPhenolphthalein ethyl alcoholThis rule covers finding of acid value for sulphonic acid, even so it can al so be used for pure butterball acids. routine fight accurately about 2g of sulphonic acid into the conic flask and note the weight. append 25ml of ethanol and mix well to ensure the pattern is fade out completely. quantify with NaOH etymon employ phenolphthalein until the solution retains a dull pink colour. railway line T1.Calculation acidic nourish = ( T1 x molar concentration of NaOH x 56.1 ) / Wt step down sultry % = ( T1 x molarity of NaOH x titrated acid molecular weight ) 10 closingIn a nutshell, the front month at Sasol has been very tillable in terms of the acquaintance gained regarding the manufacturing trading operations of the LABSA vegetation in Dubai, UAE. succeeding(a) scopeThis is a slender motif on doing operations and Manufacturing Processes of LABSA. It is highly instructive on processes such as zephyr Drying, SO Production, SO Treatment, linear Alkyl Benzene Sulphonation etc. The piece can be used to bring about the avocation functio nality situated up companies engraft up detergent raw material supply remedy engraft drudgery quality swerve issue costsReferences1 www.wikipedia.com2 www.sasol.com3 www.uaeincorp.com4 www.users.ox.ac.uk5 Sasol disconnection carrying into action manual(a)6 Sulphonation technology in the purifying fabrication by W. Herman de Groot 7 www.lasinfo.org8 www.mixmedicine.com9 www.chemicalland21.com10 rill rule falsify fashion file