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
• • 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
• • 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
  • 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 also relates to the use of a formulation comprising at least methanesulfonic acid for the removal of "beer stones” and crowns of bitter formed during the preparation and / or conservation of the product. beer..
• the beer is packaged in barrels or in bottles, or even cans.
• bitter crown or yeast ring
• beer stones are formed, which are mainly made up of calcium oxalate and various organic materials.
• the fermenter is therefore commonly soiled by two very distinct types of soiling: organic soils (mainly bitter crown) and inorganic soils (mainly “beer stones”).
• an essential aspect during the preparation of beer is to have barrels, receptacles, fermenters, pipes and other devices for transporting or staying the liquids used in the preparation of said beer, which are absolutely clean and in particular free of any trace.
• organic and inorganic soiling could cause the presence and growth of bacteria or any other elements harmful to the prepared products, or even make them unfit for consumption.
• drums are cleaned while hot (typically around 80 ° C.) using phosphoric acid, sulfuric acid being too corrosive at this temperature, as indicated above.
• a first objective of the present invention consists in providing a process for cleaning the installations used in the manufacture and storage of beer which is simpler and faster than those currently used.
• Another object of the present invention is to provide a simple and efficient method allowing both efficient cleaning of "beer stones” and crowns of bitterness.
• Yet another objective is to provide a method of cleaning the installations used during the preparation and storage of beer by means of a unique formulation allowing the removal of "beer stones” and crowns of bitterness.
• a formulation based on methanesulfonic acid makes it possible to avoid the use of several cleaning formulations, such as a formulation based on phosphoric acid and a formulation based on sulfuric acid.
• the use of a formulation based on methanesulfonic acid can also make it possible to avoid several successive washing operations and also several intermediate rinses.
• the advantages are therefore mainly savings in time, costs, productivity, energy, as well as a reduction in the number of cleaning chemicals present at 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 prohibit the discharge of phosphates.
• the method of the invention makes it possible, on the one hand, to reduce the number of cleaning steps, and on the other hand to reduce the number of acid formulations used, from two (phosphoric acid and sulfuric acid) to a single formulation. for cleaning dirt.
• the formulation used in the process of the invention being less corrosive than sulfuric acid, the latter can be used for cleaning drums when hot.
• the method of the present invention relates to the cleaning of installations used for the preparation and storage of beer.
• installation is meant the various elements commonly used in breweries, and in particular vats, barrels, fermenters, pipes, valves, bottles, cans, and others, that is to say all the elements liable to enter. in contact with beer and other liquids or solids necessary for its manufacture.
• the materials of the various components of the installation are generally chosen from stainless steel, aluminum, copper, brass, steel coated or not for example with an epoxy resin, plastic, in particular polypropylene, polyethylene, poly (vinyl chloride), glass, and others.
• the materials used for the brewery installations are chosen from stainless steel 304L or 316L, aluminum, and steel coated with epoxy resin.
• the process of the invention applies to all or only to one or more parts of the installation for manufacturing beer.
• the term “installation” designates the entire installation or only one or more parts of the installation.
• the method according to the invention comprises a possible first prewash step, intended to mechanically remove the major part of the impurities.
• the pre-washing is carried out by circulating water, alone or in combination with “shots” of an alkaline solution, preferably diluted, for example an aqueous solution of potassium or sodium hydroxide.
• shots are understood to mean the sending into the part of the installation to be cleaned of an alkaline solution, generally weakly concentrated, which we leave to act for a short time. In short time, it is understood a period ranging from a few seconds to several minutes, even a few hours.
• the washing of the installation is carried out by circulating a formulation comprising at least methanesulfonic acid.
• the cleaning formulation comprises at least methanesulfonic acid (AMS).
• the formulation comprises from 0.1% to 100% by weight of methanesulfonic acid, more generally from 0.5% to 90% by weight, in particular from 0.5% to 20% by weight of acid. methanesulphonic, and more particularly from 0.5% to 5% by weight.
• the formulation is generally an aqueous formulation which can be prepared as a concentrated mixture which is diluted by the end user.
• the formulation can also be a ready-to-use formulation, i.e. one which does not need to be diluted. It is for example possible to use methanesulfonic acid in solution at 70% by weight in water, and marketed by the Arkema company under the name Scaleva TM , ready to use or diluted with water in the proportions indicated above.
• the cleaning formulation can optionally comprise one or more additives, solvents, biocides and other rheological or texturing agents, chosen from solvents and co-solvents, thickening agents, surfactants, foaming agents, anti-foaming agents, and others known to those skilled in the art.
• methanesulfonic acid as just described is effective in cleaning the dirt present or formed in the installations used during the preparation of beer.
• methanesulfonic acid thus makes it possible to remove organic and inorganic soiling, such as carbohydrates, fats, proteins, inorganic minerals such as calcium carbonate, calcium phosphate, and other types of scale including oxalates, sulfates , hydroxides and / or sulfides, 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.
• organic and inorganic soiling such as carbohydrates, fats, proteins, inorganic minerals such as calcium carbonate, calcium phosphate, and other types of scale including oxalates, sulfates , hydroxides and / or sulfides, 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.
• Methanesulfonic acid is particularly effective in removing “beer stones” and “bitter crown” type residues as indicated above.
• the washing (or cleaning) of all or part of the installation is carried out by circulating an effective amount of a formulation comprising at least methanesulfonic acid, as has just been described.
• the term “effective amount” is understood to mean an amount allowing the elimination of all the dirt, which, if they are not correctly removed, could promote the development of bacteria.
• the method of the invention makes it possible to eliminate all types of soiling, and consequently bacteria which could be detrimental to the manufacture, preservation, flavor, texture, and non-toxicity for humans. , beer prepared in the installation and stored in kegs, bottles, cans and others.
• This quantity may vary widely, depending on the volume of the installation to be cleaned, the nature and quantity of soiling that is being wishes to eliminate, temperature and pressure of the formulation used, and the like.
• an effective amount of the acidic cleaning formulation is circulated through the installation, this circulation being established for a sufficient period of time to allow complete removal of the soiling.
• the amount of formulation and the duration of circulation will be established to allow a total removal of soiling, while observing both a minimum amount of formulation (essentially for economic and environmental reasons) and the shortest possible circulation time. (also mainly for economic reasons).
• Acid cleaning with the formulation comprising at least methanesulfonic acid as indicated above can be carried out at all temperatures, generally between 0 ° C and 100 ° C, more generally between 5 ° C and 40 ° C, typically between 5 ° C and 20 ° C in the fermenter or the guard reactor and between 60 ° C and 80 ° C in the packaging containers (barrels, bottles or cans) of the beer.
• the installation is advantageously rinsed by circulating a rinsing solution, for example with water, in a manner known from the skilled in the art.
• the washing of an installation useful for the preparation of beer is carried out in a single acid washing step, unlike the techniques known today.
• This single acid washing step makes it possible to eliminate in particular the “beer stones” as well as the crowns of bitter formed during the manufacture of said beers.
• the present invention relates to the use of a formulation comprising at least methanesulfonic acid, for the removal of "stones of beer ”and crowns of bitterness formed during the making and / or preservation of beer.
• Example 1 Cleaning of dirt obtained from an industrial must
• Brewer's yeast Saccharomyces cerevisae
• the necessary quantity of living yeast 50 mL of liquid yeast for 15 liters of wort
• Fermentation takes place at room temperature (between 15 and 25 ° C) for a period of 6 days. At the end of this time, the tank is emptied.
• a crown of bitter is observed at the liquid / air interface at the top of the cylindrical-conical vessel.
• a prewash step is carried out by circulating for 3 times 5 seconds a 1.5% alkaline solution of sodium hydroxide (pause time between circulations: 5 minutes).
• the cleaning of the dirt is carried out via the circulation of a cleaning formulation under stable and controlled hydrodynamic conditions, via a fixed spray ball (Hacke brand, type M1-1 DN8) located on the part top of the tank. More particularly, the circulation flow rate is 1400 L / min and the spray pressure is 0.2 bars relative (1.2 bars absolute), the solution being maintained at room temperature (between 15 ° C and 25 ° C). ) until all soiling has disappeared. Every 5 minutes, the circulation is interrupted in order to check that the dirt in the tank has disappeared visually. The cleaning is estimated visually and the time required to obtain a visibly clean tank is thus established.
• a fixed spray ball Heacke brand, type M1-1 DN8
• test is replicated at least 6 times (2 fermentations in 3 distinct fermentation sequences).
• Table 1 shows the times, expressed in additional or less time (minutes), necessary for the total visual removal of soiling, compared to cleaning carried out with reference formulation A (1.15% by weight of acid phosphoric).
• the acid formulation 2 according to the invention allows a time saving of 40 minutes compared to another acid formulation (formic acid) and even of 10 minutes compared to the reference formulation (phosphoric acid).
• Example 2 Cleaning of soiling obtained from a reconstituted must
• the reconstituted wort is a wort obtained by diluting a kit available on the market for the manufacture of beer (reference “Brewferm” type of beer: white beer, wheat base).
• the wort is reconstituted according to the manufacturer's instructions: diluting the wort concentrate (1 L) in 14 L of cold water and adding 750 g of sugar.
• the sachet of lyophilized yeast included in the kit is added to the reconstituted must just before the fermentation takes place.
• Table 2 shows the times expressed in additional or less time (minutes), necessary for the removal of soiling, compared to the reference formulation (1.15% by mass of phosphoric acid ).
• Example 3 Cleaning of “beer stone” type dirt (beerstone)
• This solid residue is dried for 24 hours at 40 ° C., then weighed.
• Table 3 below shows the average percentage of “beer stones” dissolved on two samples according to each cleaning formulation used:
• d 1.35, ie 0.94% by weight of pure methane sulfonic acid.
• Cleaning formulation Average% of “beer stones” dissolved on the 2 deposits 1.5% volume of formulation reference A 5 1% volume of formulation reference B 65 1% v of formulation 1 5 1% v of formulation 2 55
• the formulation based on methanesulfonic acid exhibits an efficiency in terms of removing the bitter crown similar to a formulation of phosphoric acid, as well as an efficiency similar to that of sulfuric acid, in terms stone removal from beer.
• the process of the invention makes it possible to dispense with the two acid cleaning steps (phosphoric and sulfuric) recommended until now, with a single acid cleaning formulation comprising at least one alkanesulphonic acid effective for both removal. "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) on the one hand 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.
• the solution is then filtered and the filtrate is analyzed for determination by ICP spectrometry of the calcium ions present in the solution.

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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)
• Cleaning In General (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Devices For Dispensing Beverages (AREA)

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