DK170824B1 - Process and appliance for continuously culturing micro- organisms in association with a high rate of use of gaseous substrates - Google Patents

Process and appliance for continuously culturing micro- organisms in association with a high rate of use of gaseous substrates Download PDF

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DK170824B1
DK170824B1 DK140492A DK140492A DK170824B1 DK 170824 B1 DK170824 B1 DK 170824B1 DK 140492 A DK140492 A DK 140492A DK 140492 A DK140492 A DK 140492A DK 170824 B1 DK170824 B1 DK 170824B1
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pipe
fermentation liquid
loop reactor
gas
horizontal connecting
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DK140492A
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DK140492D0 (en
DK140492A (en
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Jon M Huslid
Klaus Skovbo Jensen
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Dansk Bioprotein
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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M29/00Means for introduction, extraction or recirculation of materials, e.g. pumps
    • C12M29/18External loop; Means for reintroduction of fermented biomass or liquid percolate

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  • General Health & Medical Sciences (AREA)
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  • Apparatus Associated With Microorganisms And Enzymes (AREA)
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Description

i DK 170824 B1in DK 170824 B1

FREMGANGSMÅDE OG APPARAT TIL KONTINUERLIG DYRKNING AF MIKROORGANISMER VED HØJ UDNYTTELSE AF GASFORMIGE SUBSTRATERMETHOD AND APPARATUS FOR CONTINUOUS CULTIVATION OF MICRO-ORGANISMS AT HIGH USE OF GAS SUBSTRATES

Opfindelsen angår en fremgangsmåde til kontinuerlig dyrk-5 ning af mikroorganismer ved høj udnyttelse af gasformige substrater, ved hvilken fremgangsmåde en eller flere gasser indføres og opblandes i en fermenteringsvæske, som indbringes i en loop-reaktor, der har en topdel, en i hovedsagen lodret nedstrømsdel og en ligeledes i hovedsagen lodret op-10 strømsdel, hvilke tre dele indgår i et kredsløb for fermenteringsvæsken, som cirkuleres i loop-reaktoren af en pumpe sammen med gasser, der indføres og opblandes i fermenteringsvæsken via flere injektionssteder, hvoraf i det mindste ét injektionssted er anbragt i den øverste del af ned-15 strømsdelen tæt ved topdelen.BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a process for the continuous cultivation of microorganisms by high utilization of gaseous substrates in which one or more gases are introduced and mixed into a fermentation liquid which is introduced into a loop reactor having a top portion, a substantially vertical downstream portion and also a substantially vertical upstream portion, which three parts form part of a fermentation liquid circuit which is circulated in the loop reactor by a pump together with gases introduced and mixed into the fermentation liquid through several injection sites, at least one of which injection site is located in the upper portion of the downstream portion close to the top portion.

Fremgangsmåden ifølge opfindelsen tjener til forgæring af gasformige substrater til biomasse, især til kontinuerlig dyrkning af mikroorganismer til fremstilling af protein ud 20 fra metan eller naturgas og oxygen.The process of the invention serves to ferment gaseous substrates for biomass, particularly for the continuous cultivation of microorganisms to produce protein from methane or natural gas and oxygen.

Opfindelsen angår også et apparat til brug ved udøvelse af den omhandlede fremgangsmåde og i form af en loop-reaktor, der har en topdel, en i hovedsagen lodret nedstrømsdel og 25 en ligeledes i hovedsagen lodret opstrømsdel, hvilke tre dele indgår i et kredsløb for fermenteringsvæsken, som sammen med gasserne cirkuleres i loop-reaktoren af en pumpe, samt organer til indføring af fermenteringsvæske og gasinjektionssteder til indføring af en eller flere gasser i 30 fermenteringsvæsken, hvoraf i det mindste ét injektionssted er anbragt i den øverste del af nedstrømsdelen tæt ved topdelen .The invention also relates to an apparatus for use in the process according to the present invention and in the form of a loop reactor having a top part, a substantially vertical downstream part and a substantially vertical upstream part, which three parts are included in a circuit for the fermentation liquid. which, together with the gases, are circulated in the loop reactor of a pump, and means for introducing fermentation liquid and gas injection sites for introducing one or more gases into the fermentation liquid, at least one of which is located in the upper part of the downstream portion close to the top part .

I traditionelle tankreaktorer eller tankfermentorer sker 35 tilblandingen og optagelsen af gasformige substrater i fermenteringsvæsken ved hjælp af omrørere, der finfordeler 2 DK 170824 B1 gassen til små bobler, hvorved et stort gas/væske kontakt-areal opnås pr. volumenenhed fermenteringsvæske. Selv om man kan opnå en god homogenisering af gas-væske blandingen i denne type fermentorer, er traditionelle fermentorer ikke 5 velegnet til produktion i stor skala, når der ønskes en høj udnyttelsesgrad af gassen. Gassen passerer nemlig fermenteringsvæsken i løbet af få sekunder under sin opstigning fra en normalt i bunden af fermentoren anbragt gasdyse til væskens overflade. Derved opnår gassen ikke en tilstrækkelig 10 lang opholdstid i fermenteringsvæsken til, at en tilnærmelsesvis fuldstændig udnyttelse af gassen kan ske. Desuden har pumperne, som sædvanligvis er af propeltypen og tjener til omrøring eller cirkulation af fermenteringsvæsken i fermentoren, et stort effektforbrug udtrykt i kWatt afsat 15 effekt pr. masseenhed gas optaget i væsken.In conventional tank reactors or tank fermenters, the mixing and absorption of gaseous substrates in the fermentation liquid is effected by agitators which atomize the gas into small bubbles, thereby obtaining a large gas / liquid contact area per unit volume. volume unit of fermentation liquid. Although a good homogenization of the gas-liquid mixture can be obtained in this type of fermenters, traditional fermenters are not suitable for large-scale production when a high utilization rate of the gas is desired. Namely, the gas passes through the fermentation liquid in a matter of seconds during its ascent from a normal nozzle located at the bottom of the fermenter to the surface of the liquid. Thereby, the gas does not achieve a sufficiently long residence time in the fermentation liquid for an approximately complete utilization of the gas to occur. In addition, the pumps, which are usually of the propeller type and which serve to stir or circulate the fermentation liquid in the fermentor, have a large power consumption expressed in kWatts of 15 power per unit. mass unit of gas absorbed into the liquid.

Den bevægelse af gas/væskeblandingen, der i en normal omrørt tankfermentor foregår ved hjælp af omrørere monteret på en eller flere aksler i beholderen, kan også foregå i en 20 ringformet reaktorkonstruktion - en såkaldt loop-reaktor -hvori en tvungen cirkulation af fermenteringsvæsken tilvejebringes. Gassen indblæses normalt i bunden af et langt, lodret rør, der udgør den ene gren af loop-reaktoren. I toppen af denne gren, hvilken top benævnes loop-reaktorens 25 headspace, separeres gassen fra fermenteringsvæsken, hvorefter denne løber tilbage mod bunden i loop-reaktorens anden gren, der ligeledes er anbragt lodret. Væskecirkulationen sker oftest ved hjælp af en pumpe anbragt i et kort forbindelsesrør mellem de nederste ender af de to lodrette 30 grene i loop-reaktoren. En vis naturlig væskecirkulation sker på grund af forskellen i massefylde mellem gas/væske-blandingen i den opstigende gren og den for gas befriede fermenteringsvæske i den nedstigende gren af loop-reaktoren.The movement of the gas / liquid mixture that takes place in a normal stirred tank fermentor by means of agitators mounted on one or more shafts in the container can also take place in an annular reactor structure - a so-called loop reactor - where a forced circulation of the fermentation liquid is provided. The gas is usually blown into the bottom of a long vertical pipe forming one branch of the loop reactor. At the top of this branch, which is referred to as the headspace of the loop reactor 25, the gas is separated from the fermentation liquid, which then runs back toward the bottom of the second branch of the loop reactor, which is also arranged vertically. Fluid circulation is most often effected by means of a pump arranged in a short connecting tube between the lower ends of the two vertical branches of the loop reactor. Some natural liquid circulation occurs due to the difference in density between the gas / liquid mixture in the ascending branch and the gas-free fermentation liquid in the descending branch of the loop reactor.

3535

Gassen kan indblæses gennem dyser eller ejektorer anbragt i 3 DK 170824 B1 bunden af den opstigende gren. En god masseovergang mellem gas og fermenteringsvæske opnås i en omegn af dyserne eller ejektorerne, men gasboblerne antager hurtigt en af fermenteringsvæskens fysiske egenskaber bestemt ligevægtsstørrel-5 se, der er meget større end den, der opnås tæt ved dyserne eller ejektorerne. Herved vil masseovergangen i loop-reaktorens totale volumen oftest være meget ringe.The gas can be blown in through nozzles or ejectors located in the bottom of the ascending branch. A good mass transition between gas and fermentation liquid is achieved in the vicinity of the nozzles or ejectors, but the gas bubbles quickly assume one of the physical properties of the fermentation liquid, which is much larger than that obtained close to the nozzles or ejectors. As a result, the mass transition in the total volume of the loop reactor will usually be very low.

EP patentansøgning nr. 90610050.8, der er offentliggjort 10 som EP offentliggørelsesskrift nr. 0 418 187 Al og har prioritet fra DK patentansøgning nr. 3867/89 af den 7. august 1989, angiver en fremgangsmåde, hvor man ved anbringelse af en række statiske miksere i både den op- og nedstigende gren af en loop-reaktor opnår en gentagen dispergering af 15 gassen i fermenteringsvæsken og dermed en betydeligt højere total masseovergang i det givne fermenteringsvolumen end det tidligere har været kendt.EP Patent Application No. 90610050.8, published as EP Publication Publication No. 0 418 187 A1 and having priority from DK Patent Application No. 3867/89 of August 7, 1989, discloses a method of applying a series of static mixers in both the ascending and descending branch of a loop reactor, a repeated dispersion of the gas in the fermentation liquid achieves a significantly higher total mass transition in the given fermentation volume than previously known.

I samme patentansøgning er det også vist, hvorledes der i 20 forhold til en normal loop-reaktor kan opnås en betydeligt længere opholdstid for gassen ved at indføre gassen tæt ved toppen af den nedstigende gren af loop-reaktoren i stedet for i bunden af den opstigende gren. Gennem opfindelsen, som er omhandlet i den anførte EP patentansøgning, opnås en 25 god gas/væskekontakt i hvert enkelt volumen af fermente-ringsvoluminet samt en lang opholdstid for gassen i fermenteringsvæsken. Det på grund af de statiske miksere forøgede effektbehov opfyldes ved at benytte en større pumpe, end hvad der normalt kræves i en loop-reaktor.In the same patent application it is also shown how, in relation to a normal loop reactor, a significantly longer residence time for the gas can be obtained by introducing the gas close to the top of the descending branch of the loop reactor rather than at the bottom of the ascending branch. Through the invention disclosed in the EP patent application, a good gas / liquid contact is obtained in each volume of the fermentation volume as well as a long residence time for the gas in the fermentation liquid. The increased power requirements due to the static mixers are met by using a larger pump than is normally required in a loop reactor.

3030

Alligevel er udnyttelsen af gassen i fermenteringsvæsken ikke optimal ved den kendte fremgangsmåde, og effektbehovet synes unødvendigt stort, og det er derfor formålet med den foreliggende opfindelse at angive en sådan udformning af 35 fremgangsmåden, at gassen udnyttes i endnu højere grad end det tidligere har været muligt ved en loop-reaktor og under 4 DK 170824 B1 anvendelse af mindre effekt.Nevertheless, the utilization of the gas in the fermentation liquid is not optimal in the known process, and the power requirement seems unnecessarily large, and it is therefore the object of the present invention to provide such an embodiment of the process that the gas is utilized to an even greater extent than it has previously been. possible with a loop reactor and using less power.

Der skal også som en del af opfindelsen angives et apparat i form af en loop-reaktor til brug ved udøvelse af frem-5 gangsmåden.Also provided as part of the invention is an apparatus in the form of a loop reactor for use in the practice of the method.

Dette formål opnås ved en fremgangsmåde af den indledningsvist angivne art, hvilken fremgangsmåde ifølge opfindelsen er særegen ved, at en væsentlig del af massetransporten fra 10 gas- til væskefase og den dermed forbundne fermenteringsproces foregår i et ovalt eller på anden måde udformet rørstykke, som forløber hovedsageligt vandret ud til siden fra det af nedstrømsdelen og opstrømsdelen dannede plan mellem de nederste ender af nedstrømsdelen henholdsvis op-15 strømsdelen, og at fermenteringsvæsken cirkuleres af i det mindste én pumpe, der er anbragt i det vandret forløbende rørstykke.This object is achieved by a method of the type mentioned in the preamble, which method is peculiar in that a substantial part of the mass transport from 10 gas to liquid phase and the associated fermentation process takes place in an oval or otherwise shaped pipe piece which runs substantially horizontal to the side from the plane formed by the downstream portion and the upstream portion between the lower ends of the downstream portion and the upstream portion, respectively, and that the fermentation liquid is circulated by at least one pump disposed in the horizontally extending pipe portion.

Herved er det på grund af trykket fra den ovenstående væ-20 skesøjle i de vertikale rør muligt at overføre en særligt stor stofmængde fra gasfase til væskefase pr. tidsenhed, idet opløseligheden af gas i væsken - og dermed massetransporten - stiger proportionalt med det absolutte tryk.Hereby, due to the pressure from the above liquid column in the vertical pipes, it is possible to transfer a particularly large amount of substance from gas phase to liquid phase per minute. unit of time, since the solubility of gas in the liquid - and thus the mass transport - increases proportionally to the absolute pressure.

25 Det er herved fordelagtigt, at det hovedsageligt vandret forløbende rørstykke udgøres af et nederste horisontalt forbindelsesrør, der med sin ene ende er sluttet til den nederste ende af den lodrette nedstrømsdel og med sin anden ende er sluttet til enden af et øverste horisontalt forbin-30 delsesrør, som med sin modsatte ende er forbundet til den nederste ende af den lodrette opstrømsdel, og at pumpen udgøres af flere propellere, der fortrinsvis er anbragt i det nederste horisontale forbindelsesrør.It is advantageous hereby that the substantially horizontally extending piece of pipe is constituted by a lower horizontal connecting pipe, with one end connected to the lower end of the vertical downstream part and with its other end connected to the end of an upper horizontal connection. supply pipe, which at its opposite end is connected to the lower end of the vertical upstream portion, and that the pump is constituted by several propellers, preferably located in the lower horizontal connecting pipe.

35 En væsentlig del af massetransporten fra gasfase til væskefase og den dermed forbundne fermenteringsproces vil derved 5 DK 170824 B1 foregå i det nederste horisontale forbindelsesrør.35 A substantial part of the mass transport from gas phase to liquid phase and the associated fermentation process will thereby take place in the lower horizontal connecting pipe.

Det er endvidere fordelagtigt, at de to horisontale forbindelsesrør er parallelle, idet konstruktionsomkostningerne 5 for etablering af rørstykket og dettes understøtning derved bliver mindre, end hvis rørstykket forløb som en cirkelbue eller i en oval mellem de nederste ender af de lodrette rør i loop-reaktoren.It is further advantageous that the two horizontal connecting pipes are parallel, with the construction cost 5 for establishing the pipe piece and its support thereby being smaller than if the pipe piece ran as a circular arc or in an oval between the lower ends of the vertical pipes in the loop reactor. .

10 Det er også fordelagtigt, at der i det hovedsageligt vandret forløbende rørstykke er anbragt spredere med indbyrdes mellemrum i rørstykkets længderetning for at undgå forekomst af gasbobler over en forud fastsat størrelse.It is also advantageous for spacers to be disposed at intervals in the longitudinal direction of the substantially horizontal portion in order to avoid the presence of gas bubbles above a predetermined size.

15 Opfindelsen angår som anført ovenfor også et apparat, såsom en loop-reaktor, til brug ved udøvelse af den omhandlede fremgangsmåde, hvilket apparat ifølge opfindelsen er særegen ved, at apparatet har et ovalt eller på anden måde udformet rørstykke, som forløber hovedsageligt vandret ud til 20 siden fra det af nedstrømsdelen og opstrømsdelen dannede plan mellem de nederste ender af nedstrømsdelen henholdsvis opstrømsdelen, og at den i det mindste ene pumpe er anbragt i det vandret forløbende rørstykke.The invention also relates, as stated above, to an apparatus, such as a loop reactor, for use in carrying out the method according to the invention, which apparatus is peculiar in that the apparatus has an oval or otherwise shaped pipe piece which extends substantially horizontally. to the side 20 from the plane formed by the downstream portion and the upstream portion between the lower ends of the downstream portion and the upstream portion, respectively, and that the at least one pump is disposed in the horizontally extending pipe piece.

25 Fremgangsmåden og apparatet ifølge opfindelsen skal forklares nærmere i det følgende under henvisning til tegningen, hvor:The method and apparatus according to the invention will be explained in more detail below with reference to the drawing, in which:

Fig. 1 i perspektiv viser en udførelsesform for et appa- 30 rat ifølge opfindelsen, og fig. 2 skematisk viser et vertikalt snit langs aksen i et horisontalt anbragt rør i det i fig. 1 viste apparat.FIG. 1 is a perspective view of one embodiment of an apparatus according to the invention; and FIG. 2 schematically shows a vertical section along the axis of a horizontally arranged tube in the embodiment of FIG. 1.

35 I fig. 1 betegner 1 en udførelsesform for et apparat ifølge DK 170824 B1 e opfindelsen. Apparatet foreligger som en loop-reaktor, der har en nedstrømsdel 2 og en opstrømsdel 3, hvilke to dele 2, 3 strækker sig i hovedsagen lodret i loop-reaktorens 1 brugsstilling. Nedstrømsdelen 2 er foroven forsynet med en 5 topdel 4, der sædvanligvis kaldes headspace.35 In FIG. 1 represents 1 an embodiment of an apparatus according to the invention. The apparatus is provided as a loop reactor having a downstream portion 2 and an upstream portion 3, two portions 2, 3 extending substantially vertically in the operating position of the loop reactor 1. Downstream portion 2 is provided at the top with a top 5 portion, usually called headspace.

Topdelen 4 af loop-reaktoren 1 er tildannet som en cylinder 5 med en væsentlig større diameter end nedstrømsdelen 2, hvilken cylinder 5 er forbundet med nedstrømsdelen 2 ved 10 hjælp af et konisk overgangsstykke 6. Opstrømsdelen 3 er via en rørbøjning 7 ført tangentielt ind i siden af cylinderen 5. Denne konstruktion er med til at give en god separation af fermenteringsvæske og gasbobler under loop-reaktorens 1 drift, idet der virker centrifugalkræfter i rør-15 bøjningen 7, og i den cylindriske del 5 opstår der en kraftig cirkulation af fermenteringsvæsken med dertil hørende centrifugalkræfter. Dermed er adskillelsen af gasbobler fra fermenteringsvæsken løst på en meget fordelagtig måde.The top portion 4 of the loop reactor 1 is formed as a cylinder 5 having a substantially larger diameter than the downstream portion 2, which cylinder 5 is connected to the downstream portion 2 by means of a tapered transition piece 6. The upstream portion 3 is tangentially inserted into a pipe bend 7. side of cylinder 5. This construction contributes to a good separation of fermentation liquid and gas bubbles during the operation of the loop reactor 1, with centrifugal forces acting in the tube bend 7, and in the cylindrical part 5 a strong circulation of the fermentation liquid occurs. with associated centrifugal forces. Thus, the separation of gas bubbles from the fermentation liquid is solved in a very advantageous way.

20 Ved kendte loop-reaktorer er de nederste ender af nedstrømsdelen og opstrømsdelen forbundet med hinanden ved hjælp af et kort vandret rørs tykke, så der frembringes et lukket kredsløb, hvori fermenteringsvæske kan bringes til at cirkulere ved hjælp af en pumpe eller et lignende organ.In known loop reactors, the lower ends of the downstream portion and the upstream portion are connected to each other by the thickness of a short horizontal tube to produce a closed circuit in which fermentation liquid can be circulated by means of a pump or similar means.

2525

Ved loop-reaktoren 1 ifølge opfindelsen er den nederste ende 8 af nedstrømsdelen 2 via en rørbøjning 10 på 90° forbundet med et første forbindelsesrør 11, der strækker sig i det væsentlig vandret ud til en side bort fra det af ned-30 strømsdelen 2 og opstrømsdelen 3 dannede plan. Ved den modsatte ende af det første forbindelsesrør 11 er dette gennem endnu en rørbøjning 12, som er på 180°, sluttet til et andet forbindelsesrør 13, der ligeledes forløber i hovedsagen vandret parallelt med det første forbindelsesrør 11. Slut-35 telig er enden af det andet forbindelsesrør 13 forbundet til den nederste ende 9 af opstrømsrøret 3 ved hjælp af en DK 170824 Bl 7 rørbøjning 14 på ca. 90°. Med henvisningsbetegnelsen 16 på tegningen er angivet en af det første forbindelsesrør 11, rørbøjningen 12 og det andet forbindelsesrør 13 dannet rørsløj fe.In the loop reactor 1 according to the invention, the lower end 8 of the downstream part 2 is connected via a 90 ° pipe bend 10 to a first connecting pipe 11 which extends substantially horizontally to a side away from that of the downstream part 2 and the upstream portion 3 formed plane. At the opposite end of the first connecting pipe 11, this is connected through a second pipe bend 12, which is 180 °, to a second connecting pipe 13, which also extends substantially horizontally parallel to the first connecting pipe 11. Finally, the end of the pipe the second connecting tube 13 connected to the lower end 9 of the upstream tube 3 by means of a DK 170824 B1 pipe bend 14 of approx. 90 °. The reference numeral 16 in the drawing indicates a pipe loop fairy formed by the first connecting pipe 11, the pipe bending 12 and the second connecting pipe 13.

55

Ved hjælp af i det mindste en på tegningen ikke vist pumpe bringes en fermenteringsvæske til at strømme i loop-reaktoren 1 i den med en pil 15 viste strømningsretning.By means of at least one pump not shown in the drawing, a fermentation liquid is caused to flow in the loop reactor 1 in the flow direction indicated by an arrow 15.

10 Den nævnte rørsløjfe 16 kunne i og for sig også være tildannet som en del af en cirkelbue, en oval eller en ellipse.Said pipe loop 16 could in itself also be formed as part of a circular arc, an oval or an ellipse.

Fortrinsvis er de nedre ender 8, 9 af nedstrømsdelen 2 hen-15 holdsvis af opstrømsdelen 3 endvidere afkortet på en sådan måde, at nedstrømsdelens 2 nederste ende 8 befinder sig på et lavere niveau end opstrømsdelens 3 nederste ende 9, og det vil kunne forstås, at det første forbindelsesrør 11 derfor vil befinde sig på et lavere niveau end det andet 20 forbindelsesrør 13.Preferably, the lower ends 8, 9 of the downstream portion 2 and 15 of the upstream portion 3 are further truncated in such a way that the lower end 8 of the downstream portion 2 is at a lower level than the lower end 9 of the upstream portion 3, and it can be understood. that the first connecting pipe 11 will therefore be at a lower level than the second connecting pipe 13.

Rørene, som udgør nedstrømsdelen 2, opstrømsdelen 3 og det øverste horisontale forbindelsesrør 13, kan udføres med samme diameter som det nederste horisontale forbindelsesrør 25 11, men diametrene af rørene 2, 3, 11 og 13 kan også være forskellige. Således kan den vertikale opstrømsdel 3 og det øverste horisontale forbindelsesrør 13 udformes med mindre diameter end det nederste horisontale forbindelsesrør 11, hvorved en større del af den samlede opholdstid i loop-re-30 aktoren 1 tilbringes i det mere produktive nederste vandrette forbindelsesrør 11.The tubes constituting the downstream portion 2, the upstream portion 3 and the upper horizontal connecting tube 13 may be formed with the same diameter as the lower horizontal connecting tube 25 11, but the diameters of the tubes 2, 3, 11 and 13 may also be different. Thus, the vertical upstream portion 3 and the upper horizontal connecting pipe 13 can be formed with smaller diameter than the lower horizontal connecting pipe 11, whereby a greater part of the total residence time in the loop actuator 1 is spent in the more productive lower horizontal connecting pipe 11.

For at undgå, at gas- og væskefaserne på grund af densitetsforskelle separeres radielt ved horisontalt flow i læn-35 gere frie rørstykker, anbringes såkaldte spredere 17 med periodiske mellemrum i det nederste horisontale forbindel- 8 DK 170824 B1 sesrør 11. En spreder 17 er i denne sammenhæng defineret som en konstruktion, der er karakteriseret ved to egenskaber: 5 (a) Den splitter og fordeler gasbobler 18 over hele rørtværsnittet; (b) på udgangssiden skaber sprederen 17 hvirvler, hvis størrelse er sammenlignelig med elementets hydrau-10 liske diameter eller rørdiameteren.In order to avoid the gas and liquid phases being separated radially by horizontal flow in longer free tubes due to density differences, so-called spreaders 17 are arranged at periodic intervals in the lower horizontal connecting pipe 11. A spreader 17 is in this context defined as a structure characterized by two properties: 5 (a) It splits and distributes gas bubbles 18 over the entire pipe cross section; (b) on the output side, the spreader 17 creates swirls the size of which is comparable to the hydraulic diameter of the element or the pipe diameter.

Sprederen 17 kan for eksempel bestå af en form for disper-gator, der opfylder egenskab (a), efterfulgt af ledeskovle, der ændrer flowets lokale retning, så egenskab (b) tilgode-15 ses. Flere statiske miksere, som kombinerer de to egenskaber i en og samme geometri, findes dog kommersielt tilgængelige.For example, the spreader 17 may consist of a type of disperser that satisfies property (a), followed by guide vanes which change the local direction of flow so that property (b) is attributed. However, several static mixers combining the two properties in one and the same geometry are commercially available.

Den i praksis forekommende fordeling af gasbobler 18 efter 20 en spreder 17, der besidder egenskaberne (a) og (b), er vist skematisk på fig. 2, der viser et vertikalt snit langs aksen af et af de horisontale forbindelsesrør 11, 13 i loop-reaktoren 1 ifølge opfindelsen.The actual distribution of gas bubbles 18 after 20 of a spreader 17 having properties (a) and (b) is shown schematically in FIG. 2, showing a vertical section along the axis of one of the horizontal connecting pipes 11, 13 in the loop reactor 1 according to the invention.

25 På fig. 2 angiver Lm længden af en spreder 17 langs den nævnte akse, medens L0 angiver den strækning efter sprederen 17, inden for hvilken gasbobler 18, der er frembragt i sprederen, er tilnærmelsesvist jævnt fordelt inden for rørtværsnittet. Efter strækningen L0 vil gasboblerne 18 efter-30 hånden samle sig langs indersiden 19 af forbindelsesrørets 11, 13 overside, idet boblefronten hælder skråt fremad og op under en vinkel a. Rørtværsnittet er fastlagt ved rørdiameteren D.25 In FIG. 2, Lm denotes the length of a spreader 17 along said axis, while L0 denotes the stretch of spreader 17 within which gas bubbles 18 produced in the spreader are approximately evenly distributed within the pipe cross section. After the stretch L0, the gas bubbles 18 will eventually gather along the inside 19 of the upper side of the connecting pipe 11, 13, the bubble front inclined forwardly and upwardly at an angle a. The pipe cross-section is determined by the pipe diameter D.

35 Ved en moderat volumetrisk gasfraktion (mindre end 0,15) er afstanden L0, fortrinsvis afhængig af fermenteringsvæskens 9 DK 170824 B1 strømningshastighed og viskositet samt sprederens 17 hvirvelskabende geometri (hvirvelstørrelsen ifølge egenskab (b)). Boblefrontens hældning, a, er tilnærmelsesvist givet ved forholdet mellem gasboblernes 18 middelopstigningsha-5 stighed og væskens horisontale strømningshastighed, hvor middelopstigningshastigheden afhænger af væskens viskositet og overfladespænding. L0 og α kan enten estimeres udfra teoretiske overvejelser og modelberegninger eller findes eksperimentelt for givne fluid-mekaniske betingelser, såsom 10 holdup, viskositet, overfladespænding og strømningshastighed af væske, og for en given spredergeometri.At a moderate volumetric gas fraction (less than 0.15), the distance L0, preferably depends on the flow rate and viscosity of the fermentation liquid 9 and the vortex-creating geometry of the spreader 17 (the vortex size according to characteristic (b)). The slope of the bubble front, a, is approximately given by the ratio of the mean rise velocity of the gas bubbles 18 to the horizontal flow rate of the liquid, where the mean rise rate depends on the viscosity and surface tension of the liquid. L0 and α can either be estimated from theoretical considerations and model calculations or be found experimentally for given fluid-mechanical conditions, such as holdup, viscosity, surface tension and flow rate of liquid, and for a given spreader geometry.

Spredere 17 skal anbringes med en indbyrdes afstand hen gennem den horisontalt forløbende rørsløjfe 16 i loop-reak-15 toren 1, hvilken afstand skal afpasses, så gasboblerne 18 efter en spreder 17 stadig er fordelt over den overvejende del af rørdiameteren, D, målt i vertikal retning, hvis rørtværsnittet er ovalt. Denne indbyrdes afstand mellem på hinanden følgende spredere 17 skal være mindre end eller 20 lig med en største afstand, Lmax, som er givet ved L0 og a.Spacers 17 must be spaced apart through the horizontally extending pipe loop 16 of the loop reactor 1, which distance must be adjusted so that the gas bubbles 18 after a spreader 17 are still distributed over the predominant portion of the pipe diameter, D, measured in vertical direction if the tube cross section is oval. This spacing between successive spreaders 17 must be less than or equal to a maximum distance, Lmax, given by L0 and a.

I tilfælde af, at statiske miksere af den tidligere anførte art anvendes som spredere 17, er den mindste længde,In the case of static mixers of the kind mentioned previously as spreader 17, the minimum length is

Lm min, af en mikser givet ved, at mikseren for den givne 25 fordeling af gasboblerne 18 på indgangssiden skal opfylde egenskaben (a) på udgangssiden.Lm min, of a mixer given that the mixer for the given 25 distribution of the gas bubbles 18 on the input side must satisfy the property (a) on the output side.

Da den specifikke massetransport typisk er 5-10 gange højere i en statisk mikser end i en tilsvarende længde frit 30 rørstykke, vil den gennemsnitlige massetransport pr. reaktorvolumen kunne øges ved at øge længden Lm af den enkelte mikser udover Lm Bin og/eller ved at anbringe mikserne med mindre afstand end Lmax. Herved stiger dog også energiforbruget i form af den fornødne pumpeeffekt, idet trykfaldet 35 over en mikser er meget større end over en tilsvarende længde frit rørstykke.Since the specific mass transport is typically 5-10 times higher in a static mixer than in a corresponding length of free pipe piece, the average mass transport per reactor volume could be increased by increasing the length Lm of the individual mixer in addition to Lm Bin and / or by placing the mixers at a smaller distance than Lmax. However, this also increases the energy consumption in the form of the required pump power, since the pressure drop 35 over a mixer is much larger than over a corresponding length of free pipe.

10 DK 170824 B110 DK 170824 B1

Statiske miksere kan også anbringes med passende mellemrum i de vertikale rør, nedstrømsdelen 2 og opstrømsdelen 3, for at undgå forekomsten af gasbobler 18 over en vis forud 5 fastsat maksimal størrelse og for at øge den totale masse transport. For de vertikale rørs 2, 3 vedkommende er der ud fra et specielt radialt asymmetrisk faseseparationsmæssigt hensyn ingen øvre grænse angående afstanden mellem to på hinanden følgende miksere.Static mixers may also be placed at appropriate intervals in the vertical pipes, downstream portion 2 and upstream portion 3, to avoid the occurrence of gas bubbles 18 above a certain predetermined maximum size and to increase the total mass of transport. In the case of the vertical tubes 2, 3 there is no upper limit on the distance between two consecutive mixers from a special radially asymmetric phase separation consideration.

1010

Gasindføringen kan ske gennem på tegningen ikke viste dyser, ejektorer eller porøse filtre anbragt i det nederste horisontale forbindelsesrør 11, og der kan være et eller flere injektionssteder. Der kan også være en eller flere 15 gasindføringer i den vertikale nedstrømsdel 2, hvoraf et vil være anbragt i den øvre del af nedstrømsdelen 2 tæt under det koniske overgangsstykke 6.The gas introduction may be effected through nozzles, ejectors or porous filters not shown in the drawing located in the lower horizontal connecting tube 11, and there may be one or more injection sites. There may also be one or more gas inlets in the vertical downstream portion 2, one of which will be located in the upper portion of the downstream portion 2 just below the tapered transition piece 6.

Ved hvert injektionssted tilstræbes indblæst en sådan gas-20 mængde pr. tidsenhed, at en bestemt, ønsket opholdstid opnås i fermenteringsmediet omkring indføringsstedet.At each injection site, such a gas quantity of 20 time unit that a particular desired residence time is obtained in the fermentation medium around the insertion site.

Valget af antal og placering af injektionssteder fastsættes udfra følgende retningslinier: 25 (1) Gasindføringer udføres med tilstrækkeligt kort mellemrum langs fermentorrøret, så den faktiske lokale opholdstid i nedstrømsdelen 2 og det neder-ste horisontale forbindelsesrør 11 ikke synker me- 30 get i forhold til den ønskede, optimale værdi, og (2) en tilstrækkelig længde i relation til væskestrømningshastigheden af den sidste del af det nederste horisontale forbindelsesrør 11 holdes fri for in- 35 jektionssteder, så en ønsket gasudnyttelse er op nået ved gasboblernes ankomst til topdelen 4 i 11 DK 170824 B1 loop-reaktoren 1.The choice of number and location of injection sites is determined from the following guidelines: 25 (1) Gas introductions are made at sufficiently short intervals along the fermentor tube so that the actual local residence time in downstream portion 2 and lower horizontal connecting tube 11 does not decrease significantly relative to the desired optimum value, and (2) a sufficient length relative to the fluid flow rate of the last portion of the lower horizontal connecting tube 11 is kept free of injection sites so that a desired gas utilization is achieved upon the gas bubbles' arrival at the top portion 4 of 11 DK 170824 B1 loop reactors 1.

I tillæg til at øge det hydrostatiske tryk i det nederste horisontale forbindelsesrør 11 har de vertikale rør, ned-5 strømsdelen 2 og opstrømsdelen 3, en vigtig funktion i forbindelse med udskillelse af C02, som dannes ved fermentering med mikroorganismer. Jo længere den vertikale opstrømsdel 3 og eventuelt også det øverste horisontale forbindelsesrør 13 er, des lavere gennemsnitligt indhold af 10 opløst C02 vil der være i fermenteringsvæsken under en fermentering med samme totale massetransport. Ved fermentering af bestemte mikroorganismer, der hæmmes uhensigtsmæssigt ved høj koncentration af opløst C02, kan forholdet mellem længderne af det nederste horisontale forbindelsesrør 11 og 15 den vertikale opstrømsdel 3 derfor bruges som en vigtig designparameter .In addition to increasing the hydrostatic pressure in the lower horizontal connecting tube 11, the vertical tubes, the downstream portion 2 and the upstream portion 3, have an important function in the separation of CO 2 formed by fermentation with microorganisms. The longer the vertical upstream portion 3 and possibly also the upper horizontal connecting tube 13, the lower average content of 10 dissolved CO 2 will be in the fermentation liquid during a fermentation with the same total mass transport. Therefore, when fermenting certain microorganisms which are inappropriately inhibited by high concentration of dissolved CO 2, the ratio of the lengths of the lower horizontal connecting pipe 11 to 15 the vertical upstream part 3 can be used as an important design parameter.

Ved den omhandlede udformning af topdelen 4 som en cyklon udnyttes centrifugalkræfterne til uddrivning af gasbobler 20 fra fermenteringsvæsken.In the present embodiment of the top part 4 as a cyclone, the centrifugal forces are used to expel gas bubbles 20 from the fermentation liquid.

Indføring af mikroorganismer og fermenteringsmedium kan ske gennem rør anbragt på vilkårlige steder langs loop-reaktoren 1.Insertion of microorganisms and fermentation medium can take place through tubes located at random locations along the loop reactor 1.

2525

Kontinuerlig høst af biomasse kan ske ved aftapning på et vilkårligt sted langs loop-reaktoren 1, men denne aftapning foregår mest hensigtsmæssigt fra ydersiden af en af de nederste rørbøjninger 10, 14, hvor centrifugalkræfter bevir-30 ker, at væskestrømmens indhold af gasbobler 18 er mindst muligt.Continuous harvesting of biomass can be effected by bottling at any location along the loop reactor 1, but this bottling is most conveniently effected from the outside of one of the lower pipe bends 10, 14, where centrifugal forces cause the liquid stream content of gas bubbles 18 to be least possible.

Loop-reaktoren 1 ifølge opfindelsen er udformet specielt med henblik på kontinuerlig fermentering, men kan dog også 35 anvendes til batch-fermentering.The loop reactor 1 according to the invention is designed specifically for continuous fermentation, but can also be used for batch fermentation.

12 DK 170824 B112 DK 170824 B1

Fordelene ved fremgangsmåden og apparatet eller loop-reaktoren 1 ifølge opfindelsen skal især ses i, - at man ved hjælp af et i forhold til loop-reaktorens 1 5 totale volumen stort og horisontalt beliggende volumen kan opnå en vilkårlig stor total opholdstid for gasboblerne 18 i en fermenteringsvæske og dermed en høj gasudnyttelse pr. omløb i loop-reaktoren 1, at massetransport i den vandret beliggende rørsløjfe 16 er særligt stor som følge af det 10 hydrostatiske tryk udøvet af loop-reaktorens 1 vertikale dele, nedstrømsdelen 2 og opstrømsdelen 3, og at konstruktionsomkostningerne for den vandrette del 16 af loop-reaktoren 1 vil blive betydeligt mindre end omkostningerne ved konstruktion af et tilsvarende lodret stillet fermentorvo-15 lumen med de dertil nødvendige bære- og støttekonstruktioner, - at man ved periodisk anbringelse af spredere 17 i det ne-derste horisontale forbindelsesrør 11 kan frembringe forny- 20 et opblanding af gas og fermenteringsvæske for hver spreder og derved udnytte denne del af loop-reaktoren 1 til at undgå separation af gasbobler 18 og fermenteringsvæske, og - at man ved at følge de angivne retningslinier for udform-25 ning af sprederne 17 og antal og placering af gasdyser kan tilpasse loop-reaktorens 1 egenskaber, såsom høj/lav gasudnyttelse, energiforbrug/massetransport, til den ønskede fermentering inden for meget vide rammer.In particular, the advantages of the method and apparatus or loop reactor 1 according to the invention are to be seen in that - by means of a large volume and horizontally located volume relative to the total volume of the loop reactor 1, an arbitrary large total residence time of the gas bubbles 18 can be obtained. a fermentation liquid and thus a high gas utilization per liter. circulation in the loop reactor 1 that mass transport in the horizontally located pipe loop 16 is particularly high due to the hydrostatic pressure exerted by the vertical parts of the loop reactor 1, the downstream part 2 and the upstream part 3, and the construction costs for the horizontal part 16 of the loop - the reactor 1 will be considerably less than the cost of constructing a similarly vertical fermentor volume with the necessary supporting and supporting structures, - that by periodically placing sprinklers 17 in the lower horizontal connecting tube 11, 20 is a mixture of gas and fermentation liquid for each spreader, thereby utilizing this portion of the loop reactor 1 to avoid separation of gas bubbles 18 and fermentation liquid, and - by following the stated guidelines for designing the spreader 17 and number and location of gas nozzles can adapt the characteristics of the loop reactor 1, such as high / low gas utilization, energy consumption / mass transfer rt, to the desired fermentation within very wide limits.

Claims (8)

13 DK 170824 B113 DK 170824 B1 1. Fremgangsmåde til kontinuerlig dyrkning af mikroorganismer ved høj udnyttelse af gasformige substrater, ved hvil- 5 ken fremgangsmåde en eller flere gasser indføres og opblan-des i en fermenteringsvæske, som indbringes i en loop-reaktor (1), der har en topdel (4), en i hovedsagen lodret nedstrømsdel (2) og en ligeledes i hovedsagen lodret opstrømsdel (3), hvilke tre dele (2, 3, 4) indgår i et kreds-10 løb for fermenteringsvæsken, som cirkuleres i loop-reaktoren af en pumpe sammen med gasser, der indføres og opblan-des i fermenteringsvæsken via flere injektionssteder, hvoraf i det mindste ét injektionssted er anbragt i den øverste del af nedstrømsdelen (2) tæt ved topdelen (4), kende -15 tegnet ved, at en væsentlig del af massetransporten fra gas- til væskefase og den dermed forbundne fermenteringsproces foregår i et ovalt eller på anden måde udformet rørstykke (11, 12, 13, 16), som forløber hovedsageligt vandret ud til siden fra det af nedstrømsdelen (2) og op-20 strømsdelen (3) dannede plan mellem de nederste ender (8, 9. af nedstrømsdelen (2) henholdsvis opstrømsdelen (3), og at fermenteringsvæsken cirkuleres af i det mindste én pumpe, der er anbragt i det vandret forløbende rørstykke (11, 12, 13, 16). 25A process for the continuous cultivation of microorganisms by high utilization of gaseous substrates, by which method one or more gases are introduced and mixed into a fermentation liquid introduced into a loop reactor (1) having a top portion ( 4), a substantially vertical downstream portion (2) and also a substantially vertical upstream portion (3), which three portions (2, 3, 4) form part of a fermentation liquid circuit which is circulated in the loop reactor by a pump along with gases introduced and mixed into the fermentation liquid via several injection sites, at least one injection site located in the upper portion of the downstream portion (2) near the top portion (4), characterized by a substantial part of the mass transport from gas to liquid phase and the associated fermentation process takes place in an oval or otherwise shaped piece of pipe (11, 12, 13, 16) which extends mainly horizontally outward from that of the downstream part (2) and the upstream portion (3) formed between the lower ends (8, 9. of the downstream portion (2) and upstream portion (3), respectively), and that the fermentation liquid is circulated by at least one pump disposed in the horizontally extending pipe portion (11). , 12, 13, 16). 25 2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at det hovedsageligt vandret forløbende rørstykke (11, 12, 13, 16) udgøres af et nederste horisontalt forbindelsesrør (11), der med sin ene ende er sluttet til den nederste ende 30 (8) af den lodrette nedstrømsdel (2) og med sin anden ende er sluttet til enden af et øverste horisontalt forbindelsesrør (13), som med sin modsatte ende er forbundet til den nederste ende (9) af den lodrette opstrømsdel (3), og at pumpen udgøres af flere propellere, der fortrinsvis er an-35 bragt i det nederste horisontale forbindelsesrør (11). 14 DK 170824 B1Method according to claim 1, characterized in that the substantially horizontally extending pipe piece (11, 12, 13, 16) is constituted by a lower horizontal connecting pipe (11), with one end thereof connected to the lower end 30 (8). of the vertical downstream portion (2) and with its other end connected to the end of an upper horizontal connecting pipe (13) connected to its lower end to the lower end (9) of the vertical upstream portion (3) and is comprised of several propellers which are preferably arranged in the lower horizontal connecting pipe (11). 14 DK 170824 B1 3. Fremgangsmåde ifølge krav 1 eller 2, kendetegnet ved, at de to horisontale forbindelsesrør (11, 13) er anbragt indbyrdes parallelle.Method according to claim 1 or 2, characterized in that the two horizontal connecting pipes (11, 13) are arranged parallel to each other. 4. Fremgangsmåde ifølge ethvert af kravene 1-3, kende tegnet ved, at der i det hovedsageligt vandret forløbende rørstykke (11, 12, 13, 16) er anbragt spredere (17) med indbyrdes mellemrum i rørstykkets (11, 12, 13, 16) længderetning. 10Method according to any one of claims 1-3, characterized in that in the substantially horizontal extending piece of pipe (11, 12, 13, 16) spacers (17) are arranged at intervals of the pipe piece (11, 12, 13). 16) longitudinal direction. 10 5. Apparat til brug ved udøvelse af den i krav 1 omhandlede fremgangsmåde og i form af en loop-reaktor (1), der har en topdel (4), en i hovedsagen lodret nedstrømsdel (2) og en ligeledes i hovedsagen lodret opstrømsdel (3), hvilke tre 15 dele (2, 3, 4) indgår i et kredsløb for fermenteringsvæ sken, som sammen med gasserne cirkuleres i loop-reaktoren (I) af en pumpe, samt organer til indføring af fermenteringsvæske og gasinjektionssteder til indføring af en eller flere gasser i fermenteringsvæsken, hvoraf i det mindste ét 20 injektionssted er anbragt i den øverste del af nedstrømsde-len (2) tæt ved topdelen (4), kendetegnet ved, at loop-reaktoren (1) har et ovalt eller på anden måde udformet rørstykke (11, 12, 13, 16), som forløber hovedsageligt vandret ud til siden fra det af nedstrømsdelen (2) og 25 opstrømsdelen (3) dannede plan mellem de nederste ender (8, 9. af nedstrømsdelen (2) henholdsvis opstrømsdelen (3), og at den i det mindste ene pumpe er anbragt i det vandret forløbende rørstykke (11, 12, 13, 16).Apparatus for use in carrying out the method of claim 1 and in the form of a loop reactor (1) having a top portion (4), a substantially vertical downstream portion (2) and a substantially vertical upstream portion (2). 3) which three parts (2, 3, 4) are included in a fermentation liquid circuit which is circulated with the gases in the loop reactor (I) of a pump, as well as means for introducing fermentation liquid and gas injection sites for introducing a or more gases in the fermentation liquid, of which at least one injection site is located in the upper part of the downstream part (2) close to the top part (4), characterized in that the loop reactor (1) has an oval or otherwise formed pipe piece (11, 12, 13, 16) extending substantially horizontally outwardly from the plane formed by the downstream portion (2) and the upstream portion (3) between the lower ends (8, 9 of the downstream portion (2) and the upstream portion, respectively) (3) and that at least one pump is disposed in the horizontally extending pipe piece (11, 12, 13, 16). 6. Apparat ifølge krav 5, kendetegnet ved, at det hovedsageligt vandret forløbende rørstykke (11, 12, 13, 16) er udformet af et nederste horisontalt forbindelsesrør (II) , der med sin ene ende er sluttet til den nederste ende (8) af den lodrette nedstrømsdel (2) og med sin anden ende 35 er sluttet til enden af et øverste horisontalt forbindelsesrør (13), som med sin modsatte ende er forbundet til den 15 DK 170824 B1 nederste ende (9) af den lodrette opstrømsdel (3), og at pumpen udgøres af flere propellere, der fortrinsvis er anbragt i det nederste horisontale forbindelsesrør (11).Apparatus according to claim 5, characterized in that the substantially horizontally extending pipe piece (11, 12, 13, 16) is formed of a lower horizontal connecting pipe (II), with one end thereof connected to the lower end (8). of the vertical downstream portion (2) and with its other end 35 is connected to the end of an upper horizontal connecting tube (13) which is connected to its opposite end to the lower end (9) of the vertical upstream portion (3). ), and that the pump is comprised of several propellers, preferably located in the lower horizontal connecting pipe (11). 7. Apparat ifølge krav 5-6, kendetegnet ved, at de to horisontalt forløbende forbindelsesrør (11, 13) strækker sig indbyrdes parallelt.Apparatus according to claims 5-6, characterized in that the two horizontally extending connecting pipes (11, 13) extend in parallel. 8. Apparat ifølge ethvert af kravene 5-7, 10 kendetegnet ved, at der i det hovedsageligt vandret forløbende rørstykke (11, 12, 13, 16) er anbragt spredere (17) med indbyrdes mellemrum i rørstykkets (11, 12, 13, 16) længderetning for at undgå forekomst af gasbobler (18) over en forud fastsat størrelse. 15Apparatus according to any one of claims 5-7, 10, characterized in that spacers (17) are arranged in the substantially horizontally extending pipe piece (11, 12, 13, 16) at intervals in the pipe piece (11, 12, 13). 16) longitudinal direction to avoid the occurrence of gas bubbles (18) above a predetermined size. 15
DK140492A 1992-11-23 1992-11-23 Process and appliance for continuously culturing micro- organisms in association with a high rate of use of gaseous substrates DK170824B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7201884B2 (en) 2001-12-26 2007-04-10 E. I. Du Pont De Nemours And Company Process and apparatus for performing a gas-sparged reaction
US11331349B2 (en) 2017-08-02 2022-05-17 Norges Miljo-Og Biovitenskapelige Universitet (Nmbu) Treatment or prevention of gastrointestinal dysbiosis

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7201884B2 (en) 2001-12-26 2007-04-10 E. I. Du Pont De Nemours And Company Process and apparatus for performing a gas-sparged reaction
US11331349B2 (en) 2017-08-02 2022-05-17 Norges Miljo-Og Biovitenskapelige Universitet (Nmbu) Treatment or prevention of gastrointestinal dysbiosis
US11911418B2 (en) 2017-08-02 2024-02-27 Norges Miljo-Og Blovitenskapelige Universitet (NMBU) Treatment or prevention of gastrointestinal dysbiosis

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DK140492A (en) 1994-05-24

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