Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/02—Cleaning by the force of jets or sprays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
  • B08B3/04—Cleaning involving contact with liquid
  • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
  • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
  • B08B9/027—Cleaning the internal surfaces; Removal of blockages
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B08—CLEANING
  • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
  • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
  • B08B9/08—Cleaning containers, e.g. tanks
  • B08B9/0804—Cleaning containers having tubular shape, e.g. casks, barrels, drums
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/143—Sulfonic acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/34—Organic compounds containing sulfur
  • C11D3/3409—Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/34—Organic compounds containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

• the present invention relates to an acid cleaning process in the brewing industry, and in particular an improved acid cleaning process of the various materials used for the manufacture of beer and other related fermented beverages.
• this step consists in mixing the cereals (barley, malt (germinated barley), wheat, rice) with hot water (with temperature levels of 40 0 C to 100 0 C) and aromatics such as as hops and possibly various and varied spices. This stage makes it possible to extract cereals sugars and proteins to form what is called must;
• fermentation the clarified must, after cooling is introduced into the fermenter (usually a cylindro-conical reactor) called FVT.
• the yeast is added and the whole macerates for three to seven days at a temperature of 6 to 10 ° C. This step converts glucose and sugars into carbon dioxide and ethanol.
• the guard at the end of the fermentation, the mixture is shocked cold at 3 ° C to coagulate the yeasts and proteins. This step takes place either in the fermenter or in another tank. The resulting beer is matured in the guard reactor and clarified.
• the beer is packaged in barrels or in bottles, or even cans.
• step 3 we often observe the formation of a crown of bitter (or crown of yeast, "yeast ring” in English) at the gas phase / liquid phase interface.
• Bitter is mainly composed of organic insolubles: yeast residue, cell wall, insoluble sugars.
• fermentor bottom and on its walls form “beer stones”("beerstones” in English), which consist mainly of calcium oxalate and various organic materials.
• the fermenter is therefore commonly soiled by two types of very distinct soils: organic dirt (mostly bitter crown) and inorganic soils (mainly "beer stones”).
• an essential aspect in the preparation of beer, or other related fermented beverages is to have drums, containers, fermenters, pipes and other devices for transporting or staying liquids used in the preparation of said beer and other fermented beverages, which are absolutely clean and in particular free of any trace of organic and inorganic soiling. Indeed, such fouling could cause the presence and growth of bacteria or any other elements harmful to the prepared products, or even make them unfit for consumption.
• each reactor is washed either in a basic medium or in an acidic medium according to the step concerned for the preparation of the beer.
• the washing of the various elements of the installation used for the preparation of beer is usually carried out according to the following steps:
• A) brewing reactor basic washing with sodium hydroxide
• Pre-cleaning called “one-way” washing with clean water (removal of 10% of the soil), or in the presence of dilute soda (removal of 80-90% of the soil) in the form of Fast "shot", which allows a better elimination of soiling.
• Sodium hydroxide can not be used in large quantities because the fermentation tank contains carbon dioxide that may react with sodium hydroxide which could cause the vessel to collapse by depression;
• Cleaning with phosphoric acid generally at 1.5% by volume of a 56% by weight solution of phosphoric acid); and
• washing steps 2 and 3 are carried out successively with the aid of two different acids, each being effective for the removal of a type of soiling:
• C) guard this generally has less soil than the fermentor and in particular little or no bitter crown; therefore, most often a simple cleaning with water followed by cleaning with sulfuric acid + biocide mixture indicated above.
• the barrels are cleaned hot (typically about 80 0 C) with phosphoric acid, the sulfuric acid being too corrosive at this temperature, as indicated supra.
• a first object of the present invention to provide a method of cleaning facilities used in the manufacture and storage of beer simpler and faster than those currently used.
• Another object of the present invention is to provide a simple and effective method for both effective cleaning of "beer stones” and bitter crowns.
• Another objective is to propose a method of cleaning the facilities used in the preparation and storage of beer and other fermented drinks, by means of a single formulation allowing removal of all types of soiling, including "beer stones” and bitter crowns.
• an alkanesulfonic acid-based formulation makes it possible to avoid the use of several cleaning formulations, such as a phosphoric acid-based formulation and a sulfuric acid-based formulation.
• the use of an alkanesulfonic acid-based formulation may also make it possible to avoid several successive washing operations and also several intermediate rinses.
• the benefits are mainly a saving of time, costs, productivity, energy, and a decrease in the number of cleaning chemicals present on the manufacturing site.
• the phosphoric acid usually used is released in the form of phosphates, which can harm the environment, and increasingly stringent environmental standards aim to outlaw phosphate releases.
• a first object of the invention consists of a cleaning process of an installation used in the preparation of beer, or other related fermented beverages, comprising the steps of: a) optional prewashing of the installation; b) washing the plant by circulating in said plant an effective amount of a formulation comprising at least one alkanesulfonic acid; and c) rinsing the installation by circulation of a rinsing solution.
• the method of the invention allows on the one hand to reduce the number of cleaning steps, and on the other hand to reduce the number of acid formulations used, two (phosphoric acid and sulfuric acid) to a single cleaning formulation of soiling.
• the formulation used in the process of the invention being less corrosive than sulfuric acid, it can be used for cleaning hot barrels.
• the method of the present invention relates to the cleaning of facilities used for the preparation and storage of beer and other related fermented beverages.
• installation means the various elements commonly used in breweries, including vats, barrels, fermenters, pipes, valves, bottles, cans, and other, that is to say, all elements likely to come into contact with the beer and other liquids or solids necessary for its manufacture.
• the materials of the various components of the installation are generally selected from stainless steel, aluminum, copper, brass, steel coated or not, for example by an epoxy resin, plastic, in particular polypropylene , polyethylene, poly (vinyl chloride), glass, and others.
• the materials used for brewery installations are selected from 304L or 316L stainless steel, aluminum, and steel coated with epoxy resin.
• the process of the invention applies to all or only one or more parts of the beer manufacturing facility or other related fermented beverages.
• installation refers to the entire installation or one or more parts of the installation.
• the method according to the invention comprises a possible first prewash stage, intended to remove mechanically most of the impurities.
• the prewash is carried out by circulation of water, alone or in combination with "shots" of an alkaline solution, preferably diluted, for example an aqueous solution of potassium hydroxide or sodium hydroxide.
• shots preferably diluted, for example an aqueous solution of potassium hydroxide or sodium hydroxide.
• shots sending in the part of the installation to clean with an alkaline solution, usually weakly concentrated, that we let act for a short time. In short time, it is understood a period ranging from a few seconds to several minutes or even hours.
• the washing of the installation is carried out by circulation of a formulation comprising at least one alkanesulfonic acid.
• alkanesulfonic acid is preferably alkanesulfonic acids comprising a saturated hydrocarbon chain, linear or branched, having from 1 to 4 carbon atoms.
• the alkanesulphonic acids that can be used in the process of the present invention are especially chosen from methanesulphonic acid, ethanesulphonic acid, n-propanesulphonic acid, / nonspropanesulphonic acid, n-butanesulphonic acid and the acid. N-butanesulfonic acid, sec-butanesulfonic acid, tert-butanesulfonic acid, and mixtures of two or more of them in all proportions.
• the alkanesulphonic acid used in the process of the present invention is methanesulphonic acid or ethanesulphonic acid, very preferably the acid used is methanesulphonic acid.
• the cleaning formulation comprising at least one alkanesulfonic acid used in the process of the invention comprises one or more linear or branched chain alkanesulfonic acids comprising from 1 to 4 carbon atoms, and preferably comprises at least one less methanesulfonic acid (AMS).
• AMS methanesulfonic acid
• the formulation comprises from 0.1% to 100% by weight of alkanesulfonic acid, more generally from 0.5% to 90% by weight, in particular from 0.5% to 20% by weight. alkanesulfonic acid, and more particularly from 0.5% to 5% by weight.
• the formulation is generally an aqueous formulation that can be prepared as a concentrated mixture that is diluted by the end user.
• the formulation may also be a ready-to-use formulation, i.e., which does not need to be diluted. It is possible, for example, to use methanesulphonic acid in solution at 70% by weight in water and marketed by the Arkema under the name Scaleva TM, ready for use or diluted with water in the proportions indicated above.
• the cleaning formulation may optionally comprise one or more additives, solvents, biocides and other rheological or textural agents chosen from solvents and co-solvents, organic or inorganic acids (for example sulfuric acid, phosphoric, nitric, sulfamic, citric), thickening agents, surfactants, foaming agents, antifoam agents, and others known to those skilled in the art.
• solvents for example sulfuric acid, phosphoric, nitric, sulfamic, citric
• thickening agents for example sulfuric acid, phosphoric, nitric, sulfamic, citric
• surfactants for example sulfuric acid, phosphoric, nitric, sulfamic, citric
• foaming agents for example foaming agents, antifoam agents, and others known to those skilled in the art.
• alkanesulfonic acids as just described are effective in cleaning the soils present or formed in the facilities used in the preparation of beer and other fermented related drinks.
• alkanesulfonic acids thus eliminates organic and inorganic soils, such as carbohydrates, fats, proteins, inorganic minerals such as calcium carbonate, calcium phosphate, and other types of scale comprising oxalates, sulphates, hydroxides and / or sulphides, whether or not combined with various organic materials and / or metals, metalloids, alkalis or alkaline earth metals, and other residues encountered in the preparation of beer or other related fermented beverages.
• the alkanesulfonic acids are particularly effective in removing residues such as "beer stones" and "bitter crown” as indicated above.
• the washing (or cleaning) of all or part of the installation is carried out by circulation of an effective amount of a formulation comprising at least one alkanesulfonic acid, as just described.
• Effective amount means an amount for the removal of all soils, which, if not properly removed, could promote the development of bacteria.
• the process of the invention makes it possible to eliminate all types of soiling, and consequently the bacteria that could adversely affect the manufacture, the preservation, the flavor, the texture, and the non-toxicity for humans.
• an effective amount of the acidic cleaning formulation is circulated in the installation, this circulation being established for a period of time sufficient to allow complete removal of soiling.
• the amount of formulation and the circulation time will be established to allow total removal of dirt, while observing both a minimum amount of formulation (mainly for economic and environmental reasons) and a circulation time of shortest possible (also mainly for economic reasons).
• the acid cleaning with the formulation comprising at least one alkanesulfonic acid as indicated above can be carried out at all temperatures, generally between 0 0 C and 100 0 C, more generally between 5 ° C and 40 0 C, typically between 5 ° C and 20 ° C in the fermenter or the guard reactor and between 60 0 C and 80 0 C in the packaging containers (drums, bottles or cans) of beer or other fermented related drink.
• the installation is advantageously rinsed by circulation of a rinsing solution, for example with water, in a manner known per se. skilled person.
• washing a facility useful for the preparation of beer or other related fermented beverages is carried out in a single step of acid washing, unlike the techniques known today.
• This single stage of acid washing eliminates in particular "Beer stones” and bitter crowns formed during the manufacture of said beer and other related fermented beverages.
• the present invention relates to the use of a formulation comprising at least one alkanesulfonic acid, in particular at least methanesulfonic acid, for the removal of organic and inorganic soils, such as hydrates of carbon, fats, proteins, inorganic minerals such as calcium carbonate, calcium phosphate, and other types of scale including oxalates, sulphates, hydroxides and / or sulphides, whether or not combined with various organic materials and / or metals, metalloids, alkalis or alkaline earth, and other residues encountered in the preparation of beer or other related fermented beverage.
• organic and inorganic soils such as hydrates of carbon, fats, proteins, inorganic minerals such as calcium carbonate, calcium phosphate, and other types of scale including oxalates, sulphates, hydroxides and / or sulphides, whether or not combined with various organic materials and / or metals, metalloids, alkalis or alkaline earth, and other residues encountered in
• the invention relates to the use of a formulation comprising at least one alkanesulfonic acid, in particular at least methanesulfonic acid, for the elimination of "beer stones” and bitter crowns formed. during the development and / or preservation of beer.
• other fermented related drinks means any type of beverage such as for example wine, cider, whiskey, sake, and more generally any type of alcoholic beverages whose manufacturing process implements yeasts or any other aerobic fermentation capable of releasing carbon dioxide.
• the brewer's yeast Sacharomyces cerevisae
• the brewer's yeast is then introduced respecting the necessary amount of live yeast (50 ml of liquid yeast for 15 liters of must) and to be placed in industrial conditions.
• the fermentation takes place at room temperature (between 15 and 25 0 C) for a period of 6 days.
• the tank is drained.
• a crown of bitter is observed at the liquid / air interface in the top of the cylindro-conical tank.
• a prewashing step is carried out by circulation of 3 times 5 seconds of an alkaline solution to 1, 5% of sodium hydroxide (pause time between circulation: 5 minutes).
• Cleaning the dirt is achieved via the circulation of a cleaning formulation in stable and controlled hydrodynamic conditions, via a fixed spraying ball (Brand Packe, type M1-1 DN8) located on the upper part of the tank. More particularly, the flow rate is 1400 L / min and the spray pressure is 0.2 bar relative (1.2 bars absolute), the solution being maintained at room temperature (between 15 ° C and 25 0 C) until total disappearance of the stains. Every 5 minutes, the circulation is interrupted to check the disappearance of the eye from the dirt in the tank. The cleaning is estimated visually and the time required to obtain a visibly clean tank is thus established.
• a fixed spraying ball Brand Packe, type M1-1 DN8
• test is replicated at least 6 times (2 fermentations in 3 distinct fermentation sequences).
• test sequence a standard reference cleaning system based on two tanks for cleaning by the usual procedure with a solution at 1, 5% by volume of phosphoric acid at 56% by mass.
• the acid formulations used are the following:
• Table 1 shows the durations, expressed in time (minutes) extra or less, necessary for the total visual removal of soiling, compared to a cleaning performed with reference formulation A (1, 15% by mass). phosphoric acid).
• the acid formulation 2 according to the invention allows a time saving of 40 minutes compared to another acid formulation (formic acid) and even 10 minutes compared to the reference formulation (phosphoric acid).
• EXAMPLE 2 Cleaning of dirt obtained from a reconstituted must The reconstituted must is a must obtained by dilution of a commercially available kit for the manufacture of beer (reference "Brewferm” type of beer: white beer , wheat base). The must is reconstituted according to the manufacturer's instructions: dilution of the must concentrate (1 L) in 14 L of cold water and addition of 750 g of sugar. The lyophilized yeast sachet included in the kit is added to the reconstituted must just before fermentation.
• a commercially available kit for the manufacture of beer reference "Brewferm" type of beer: white beer , wheat base.
• the must is reconstituted according to the manufacturer's instructions: dilution of the must concentrate (1 L) in 14 L of cold water and addition of 750 g of sugar.
• the lyophilized yeast sachet included in the kit is added to the reconstituted must just before fermentation.
• Example 1 In contrast to the industrial must, the initial level of soiling is lower with reconstituted must and the prewashing step is not necessary; the acid cleaning is therefore carried out directly, as in step c) of Example 1.
• Table 1 Table 2 below shows the durations expressed in additional or less time (minutes) required. to the elimination of soiling, compared to the reference formulation (1, 15% by mass of phosphoric acid).
• Example 3 Beerstone Soil Cleaning
• Two representative samples of "beer stones” were taken in breweries from fermentation tanks and subjected to the following experiment: precise weighing of about 0.5 grams of deposits previously dried in air for 24 hours at 40 0 C; immersion without stirring in the test formulation brought to room temperature (between 15 ° C and 25 ° C) for 4 hours; filtration of the liquid solution and recovery of the undissolved solid. This solid residue is dried for 24 hours at 40 0 C, and then weighed.
• Table 3 shows the average percentage of "beer stones” dissolved on two samples according to each cleaning formulation used:
• the formulation based on methanesulfonic acid has an effectiveness in terms of elimination of the bitter crown similar to a phosphoric acid formulation, and an efficiency similar to that of sulfuric acid. , in terms of elimination of beer stones.
• the method of the invention eliminates the two acid cleansing steps (phosphoric and sulfuric) recommended so far, with a single acid cleaning formulation comprising at least one alkanesulfonic acid effective for elimination both "beer stones" and the crown of bitter.
• EXAMPLE 4 Dissolution Efficiency of Calcium Oxalate Calcium oxalate (6 g) is placed in 100 g of a solution of methanesulfonic acid (4 g / L and 12 g / L). one part and in 100 g of a solution of phosphoric acid (4 g / l and 12 g / l) on the other hand, for 24 hours at 70 ° C. [0075] The solution is then filtered and the filtrate is analyzed for ICP spectrometric determination of the calcium ions present in the solution. The results are shown in Table 4 below:

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Mechanical Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Cleaning By Liquid Or Steam (AREA)
• Detergent Compositions (AREA)
• Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Cleaning In General (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Devices For Dispensing Beverages (AREA)

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