WO2003035248A1 - Procede de recuperation d'un adjuvant de filtration provenant de l'extraction de polysaccharides - Google Patents

Procede de recuperation d'un adjuvant de filtration provenant de l'extraction de polysaccharides Download PDF

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Publication number
WO2003035248A1
WO2003035248A1 PCT/ES2002/000507 ES0200507W WO03035248A1 WO 2003035248 A1 WO2003035248 A1 WO 2003035248A1 ES 0200507 W ES0200507 W ES 0200507W WO 03035248 A1 WO03035248 A1 WO 03035248A1
Authority
WO
WIPO (PCT)
Prior art keywords
gases
combustion
aid according
recovery
organic matter
Prior art date
Application number
PCT/ES2002/000507
Other languages
English (en)
Spanish (es)
Inventor
Fernando Galatas Rovira
Felix Antonio LÓPEZ GÓMEZ
Aurora LÓPEZ DELGADO
Original Assignee
Hispanagar, S.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from ES200102378A external-priority patent/ES2186590B1/es
Application filed by Hispanagar, S.A. filed Critical Hispanagar, S.A.
Publication of WO2003035248A1 publication Critical patent/WO2003035248A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B01J20/106—Perlite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425

Definitions

  • the invention relates to a device that allows the partial recovery of a filter aid, used in the polysaccharide extraction processes from algae. Scope
  • Seaweeds are known as an important source of polysaccharides of great interest due to their application in fields ranging from health and human nutrition to the use as laboratory reagents and base of the most commonly used culture broths.
  • agar derives from the Malay agar-agar, through English. It is a colloid (phycocolloid) that is extracted from the marine algae of the genus Gelidium and other agarophytes (genera Acanthopeltis, Ceramium, Pterocladia, Ahnfeltia and Gracilariá), all of them belonging to the red algae (Rhodophycea order) of which more than forty species from which agar can be obtained. Commercially it comes in the form of powder, sheets, rectangular blocks and thin strips.
  • Agar is the sulfuric ester of a linear galactane. It consists of a long chain of n-galactopyranose residues linked by links of 1,3-glycosides; the chain ends at the reducing end with a residue of l-galactopyranose. Linked to the rest of the chain through carbon 4, the rest of I-galactose is esterified at carbon 6 with sulfuric acid. There are probably at least 53 galactose units attached to each SO H group, and at least 140 of these units attached to each non-reducing terminal group.
  • the constitution of the agar molecule can be represented according to Jones and Peat [W.G.M. Jones and S. Peat, J. Chem. Soc, 225 (1942)] by the following formula:
  • the agar In its natural state, the agar forms part of the cell wall of the agarophytes, probably in the form of calcium salt or a mixture of calcium or magnesium salts.
  • agar Although insoluble in cold water, the agar retains up to 20 times its weight of water but dissolves quickly in hot water. A 1% agar solution solidifies around 40 ° C, although due to high hysteresis it only melts at 95 ° C, a difference that varies according to the type of agar.
  • a stage of the process that is common to most of them This is the filtration stage.
  • the polysaccharide solution resulting from the washing and extraction or digestion stages is passed through a filter, in order to eliminate the substances that have been entrained from the previous stages and remain in suspension.
  • a filter aid is used.
  • a clarified polysaccharide solution and a sludge containing the solid used as a filter aid are obtained.
  • the sludge obtained which contains a large amount of water, is usually sent to landfill with the consequent expenses. From the environmental point of view, its use and, especially, the recovery of the auxiliary agent is of great interest, therefore the saving of raw materials (sands of great value due to their special characteristics) and the minimization of the generated waste. In addition to the undoubted economic repercussion.
  • the object of the present invention is the use of this residue and the recycling of the auxiliary agent.
  • the technique of Regeneration includes the following stages: using the filter residue as raw material, adding a certain proportion of an auxiliary material; the mixture is introduced into a calcination oven in order to remove water and carbonaceous material; the temperature is then raised for sintering. The product is ground and classified, recovering 90% of the adjuvant, which can be reused more than eight times.
  • the invention also encompasses the knowledge that volatilization of the organic components should not take place in the stream-drying apparatus because, if it were otherwise, troublesome deposits would occur in the solids filter and additional expensive purification of the waste exhaust gases would be necessary "). It has been verified that, apart from the fact that the combustion gases do not necessarily have to be used in the pre-drying, the fundamental thing is that the solid to be treated is kept between 500 and 600 ° C, as soon as possible at a temperature of 600 ° C, in order not to deteriorate the resulting product in the characteristics that give it its quality as a contributing agent.This limitation in the treatment temperature means that the volatilized gases are burned separately with a strong excess of air. Two documents, it is enough to read the summary, to verify that it is a different solution to that of the present invention. nvention The procedure object of the invention comprises the following steps:
  • the temperature of the heating stage is maintained between
  • Figure 1 shows the curves corresponding to the thermal analysis of the sludge from an agar production plant. (The sludge had previously been removed at 110 ° C). The upper graph gives the DS (differential scanning calorimetric analysis) and the lower graph gives the TGA (thermogravimetric analysis).
  • FIG. 2 shows the scheme of the process, in which the decomposition gases of the organic matter are burned in the oven itself:
  • FIG. 3 shows the scheme of the process, in which the decomposition gases of the organic matter are burned outside the oven:
  • Figure 4 shows the scheme of the pilot plant
  • Figure 5 shows the filtering curves of the adjuvant
  • Figure 6 shows the scheme of the procedure, in a second variant
  • Figure 7 shows the scheme of a pilot plant, in a second variant.
  • the numerical references correspond to the following parts and elements:
  • the filter aid used in the polysaccharide manufacturing process is a siliceous product formed by amorphous (periite) silica with impurities, mainly of alumina (probably a sodium silicoaluminate, also amorphous) and Fe 2 O 3 . Its density is 2.3 g-cm "3 and its grain size corresponds to an average size of about 80 ⁇ m.
  • the cake When the filter layer is clogged, the cake is made up of the adjuvant and a mixture of polysaccharides and a mucilaginous substance that retains on the order of 90% water. Once the cake is dry, it is formed by approximately 81% of the adjuvant, 17% of organic matter and 2% of chloride and calcium oxide. Organic matter is made up of a cellulosic substance with 41% C; the presence of sulfur (of the order of 2.5%) is possibly due to retained agar residues.
  • cellulose decomposes heterogeneously into liquid and solid fragments; As the reaction progresses, the liquid fragments or tars decompose into carbonaceous products and volatile gases, some of which are flammable and some of which are not.
  • volatile products such as ⁇ -glucosan, ethylene, water, monoxide and carbon dioxide and methane has been verified.
  • thermogram detects only the exothermic effect of the corresponding decomposition and oxidation
  • the drying air stream produces a certain amount of fines, which, given the gas temperature at the outlet (less than 100 ° C), can be collected in a bag filter 2. Both the bottom product from the dryer as well as the fines collected in the bag chamber 2, pass to a mixer 3, which in turn feeds a fluidized bed furnace 4.
  • the fluidized bed homo is of the conventional type. It consists of a grill formed by a large number of nozzles that evenly distribute the air that is blown through the bottom of the oven;
  • the mission of this air is to keep the dry material in fluidization and, taking advantage of the 700 kJ / kg that develop as a consequence of the decomposition and partial combustion of the cellulosic product, to maintain a temperature of 600 ° C in the bed.
  • the temperature of the bed is adjusted by the flow of dry product (kg / h) which is loaded in the oven.
  • the Heat can be preceded by a device for washing and final cooling of gases, a device that, depending on the size of the installation, can replace the heat recovery unit.
  • a device for washing and final cooling of gases a device that, depending on the size of the installation, can replace the heat recovery unit.
  • FIG. 3 An alternative to this process, depending on the available technology, is shown in Figure 3.
  • the process up to the fluidized bed furnace, 4, is the same as described. The difference is that secondary air is not used in the kiln here, so the fines that go to cyclone, 5, can be recyclable.
  • an additional equipment consisting of a blower, 8, is introduced into the process, which compresses the flammable gases and sends them to a burner, 9 (it can be a venturi-type burner with one or more nozzles). In it, flammable gases are burned with excess air; the hot gases formed pass, as in the process of figure 2, to the heat recovery unit, 6, and to the bag chamber, 7.
  • Example 1 Pilot plant In the fluidized bed furnace 10, to facilitate the introduction of the feed, the grill has been replaced by a conical bottom.
  • the feed is discharged, by means of a worm screw 27, into the air intake duct.
  • the height of the bed is fixed by the length of tube 19 that allows its discharge; the bed temperature is measured by means of a pyrometric rod 22 inserted into the bed.
  • the lower part of the oven (corresponding to the part where the bed is kept) is heated by a heating blanket 17, while the rest of the oven has a coating insulating protector 16.
  • the gases pass from the furnace to a cyclone 12 where they leave most of the dust that they carry and finally they are burned at the exit through a pilot flame 13.
  • the feed which has previously been dried in a stove at 110 ° C, is loaded into a double hopper system to prevent gases from escaping to the outside, since the system works at pressure above atmospheric pressure.
  • the two hoppers 24 and 26 are separated by a valve 25 that is closed while the upper hopper is loaded, after removing the plug 23; the lower hopper 26 is transparent to be able to measure the feeding speed (which is controlled by the speed of the endless screw 27) and to know when a new batch has to be loaded by unloading the upper hopper 24 through valve 25.
  • the air flow which is measured by a rotameter not shown in the figure, is a constant that is determined experimentally.
  • the overflow and cyclone products are collected in two containers 21 and 18. By closing the valves 20 and 15, the escape of gases is avoided in the period of time that the change of containers lasts.
  • the bed is loaded with the unused adjuvant; Fluidization is initially done with nitrogen to prevent an air chamber from forming in the upper part of the furnace. Heating is then started electrically until they reach 600 ° C in the bed; at that moment, maintaining the nitrogen flow, the product to be treated (dry used adjuvant) begins to load and gradually the nitrogen flow is replaced by the same air flow.
  • the gases at the outlet meet the pilot flame 13, which ignites the exhaust gases when they start to carry flammable volatiles.
  • the dimensioning of the furnace is such that the residence time of the material in the bed is 1 h. Therefore, the first 4 hours are taken as transitional time. From this time, the containers 21 and 18 are replaced by other vacuums that collect the treated products.
  • Example 2 Filterability feeds.
  • Figure 6 shows the comparative curves of the new adjuvant (curve 1) and the used one (curve 3). Among them, and very close to the first one, is the filtration curve of the adjuvant used and treated in the pilot plant described in the previous example.
  • a hot air drying is necessary first due to the high moisture content of the product to be treated (of the order of 900 kg / t).
  • the calorific value of the drying air it is convenient to carry out this operation in a counter-current tunnel 101.
  • the exhaust gases from the rotary kiln can be used, plus those coming from the heat recovery of the regenerated coadjuvant.
  • the rotary kiln 102 consists of an inclined cylinder provided with radial blades that facilitate the mixing of the solid. Externally it is covered with a layer of insulation, covered in turn by a cylinder concentric to the first.
  • the feeding of the adjuvant to be regenerated is carried out continuously by means of a cooled auger 106.
  • the residence time is regulated. This inclination in turn allows the product to be unloaded.
  • Control of the system is carried out by means of temperature sensors housed in a pyrometric reed connected throughout the reactor.
  • the output signals are sent to the control system that acts on the manipulated variable.
  • Air is introduced through the front of the equipment, by means of a blower 105 fitted with pressure and flow regulators.
  • Figure 7 shows the scheme of a pilot plant used to check the effectiveness of the improvements that are the object of the present invention.
  • the device consists of an internal cylinder 107 provided with radial blades, which facilitate mixing of the solid. Externally it is covered with an insulating layer 112, covered in turn by a cylinder concentric to the first.
  • the feed which has been previously dried in a stove at 105 ° C to constant weight, is introduced into the rotary kiln through a hopper 108.
  • the front of the equipment ends in a conical reduction to facilitate air entry. While the rear part has a removable cover that facilitates the discharge of the solid to the product collection collector 109. In it, a grid has been concentrically arranged, in order to prevent the exit of the solid and, at the same time, allow the gas outlet.
  • the heating system 113 consists of a series of resistors uniformly distributed between the insulator and the internal cylinder 107.
  • the system is controlled by two thermocouples connected to the input and output of the rotating drum, the signal from the output thermocouple is sent to a PID that acts on a variable voltage regulator.
  • the connection of the resistors is made with a rotary connector, while the thermocouples are introduced by means of a pyrometric rod 111 along the axis of the cylinder.
  • Air is introduced through a blower 110 equipped with pressure and flow regulators.
  • the connection to the equipment is also made by means of a pneumatic rotary connector 115, which is attached to a nozzle provided with resistors that allow the air at the inlet to be preheated.
  • This entire system is supported on four cylinders that allow its rotation, coupled to a variable frequency motor 114.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Drying Of Solid Materials (AREA)

Abstract

L'invention a trait à un procédé de récupération partielle d'un adjuvant de filtration que l'on utilise dans les procédés d'extraction de polysaccharides à partir d'algues consistant principalement à sécher le résidu afin d'éliminer la plus grande partie d'eau, à chauffer le produit sec à une température comprise entre 500 et 900° C et à effectuer la combustion des gaz provenant de la pyrolyse de la matière organique. Selon une première variante, le chauffage de produit sec est effectué dans un four à lit fluidisé (4), à une température avoisinant les 600° C, et l'air de fluidisation est utilisé pour chasser les gaz inflammables et détruire la matière organique résiduelle. Selon une seconde variante, on utilise, au lieu d'un four à lit fluidisé, un four rotatif à une température avoisinant les 700° C et ce pendant un temps de séjour proche des 30 minutes, ce qui permet de tirer profit des gaz s'échappant du four rotatif à l'étape de séchage (I) antérieure.
PCT/ES2002/000507 2001-10-26 2002-10-25 Procede de recuperation d'un adjuvant de filtration provenant de l'extraction de polysaccharides WO2003035248A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ESP200102378 2001-10-26
ES200102378A ES2186590B1 (es) 2001-10-26 2001-10-26 Procedimiento de recuperacion de un coadyuvante de filtracion procedente de la extraccion de polisacaridos.
ESP200202437 2002-10-22
ES200202437A ES2206048B1 (es) 2001-10-26 2002-10-22 Mejoras en el objeto de la patente de invencion p200102378 por "procedimiento de recuperacion de un coadyuvante de filtracion procedente de la extraccion de polisacaridos.

Publications (1)

Publication Number Publication Date
WO2003035248A1 true WO2003035248A1 (fr) 2003-05-01

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PCT/ES2002/000507 WO2003035248A1 (fr) 2001-10-26 2002-10-25 Procede de recuperation d'un adjuvant de filtration provenant de l'extraction de polysaccharides

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CN (1) CN1596148A (fr)
WO (1) WO2003035248A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD288317A5 (de) * 1989-10-17 1991-03-28 Veb Wtoez D. Brau- U. Malzindustrie,De Verfahren zur wiederaufbereitung von kieselgurschlaemmen aus filtrationsprozessen zum zwecke des wiedereinsatzes des regenerates
ES2036084T3 (es) * 1989-09-20 1993-05-01 Tremonis Gesellschaft Mit Beschrankter Haftung Brauerei-Nebenerzeugnisse Isntalacion para la preparacion de un fango de filtracion consistente principalmente en tierra de diatomeas y procedimiento para el funcionamiento de la instalacion.
DE19629848A1 (de) * 1995-08-01 1997-02-06 Wtu Waermetech & Umweltschutz Anordnung zur Veredelung und Regenerierung von vorwiegend Kieselgur enthaltenden Materialien

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2036084T3 (es) * 1989-09-20 1993-05-01 Tremonis Gesellschaft Mit Beschrankter Haftung Brauerei-Nebenerzeugnisse Isntalacion para la preparacion de un fango de filtracion consistente principalmente en tierra de diatomeas y procedimiento para el funcionamiento de la instalacion.
DD288317A5 (de) * 1989-10-17 1991-03-28 Veb Wtoez D. Brau- U. Malzindustrie,De Verfahren zur wiederaufbereitung von kieselgurschlaemmen aus filtrationsprozessen zum zwecke des wiedereinsatzes des regenerates
DE19629848A1 (de) * 1995-08-01 1997-02-06 Wtu Waermetech & Umweltschutz Anordnung zur Veredelung und Regenerierung von vorwiegend Kieselgur enthaltenden Materialien

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Publication number Publication date
CN1596148A (zh) 2005-03-16

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