CA2025740A1 - Process for producing hydrogen-containing gas - Google Patents
Process for producing hydrogen-containing gasInfo
- Publication number
- CA2025740A1 CA2025740A1 CA002025740A CA2025740A CA2025740A1 CA 2025740 A1 CA2025740 A1 CA 2025740A1 CA 002025740 A CA002025740 A CA 002025740A CA 2025740 A CA2025740 A CA 2025740A CA 2025740 A1 CA2025740 A1 CA 2025740A1
- Authority
- CA
- Canada
- Prior art keywords
- steam
- conversion
- heat
- gas
- oxygen
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 239000007789 gas Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 title claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011551 heat transfer agent Substances 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 229960003903 oxygen Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 101100126167 Escherichia coli (strain K12) intD gene Proteins 0.000 description 2
- 241001208007 Procas Species 0.000 description 2
- 241001074088 Urophycis Species 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- 241000324343 Causa Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- 102100038353 Gremlin-2 Human genes 0.000 description 1
- 101001032861 Homo sapiens Gremlin-2 Proteins 0.000 description 1
- 241001508691 Martes zibellina Species 0.000 description 1
- JEYCTXHKTXCGPB-UHFFFAOYSA-N Methaqualone Chemical compound CC1=CC=CC=C1N1C(=O)C2=CC=CC=C2N=C1C JEYCTXHKTXCGPB-UHFFFAOYSA-N 0.000 description 1
- 101100219263 Petunia hybrida C4H1 gene Proteins 0.000 description 1
- 101100536893 Schizosaccharomyces pombe (strain 972 / ATCC 24843) thi9 gene Proteins 0.000 description 1
- 101100152611 Sorghum bicolor CYP73A33 gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960005419 nitrogen Drugs 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- IEDVJHCEMCRBQM-UHFFFAOYSA-N trimethoprim Chemical compound COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 IEDVJHCEMCRBQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/148—Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Cosmetics (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
PROCESS FOR PRODUCING HYDROGEN-CONTAINING GAS
ABSTRACT
The production of a hydrogen-containing gas is effected by mixing a hydrocarbon feedstock with steam, a preliminary steam catalytical conversion of the resulting steam-gas mix-ture, followed by a primary catalytical conversion and a secondary steam-oxygen catalytical conversion. The secondary conversion is carried out with the supply of an oxygen-containing gas mixed with a heat-transfer agent in a volume ratio of the heat-transfer agent to oxygen equal to 0.5:30.0 and heated to a temperature of not more than 900°C. The desired product obtained in the secondary conversion is deli-vered to the primary conversion for carrying out the process of a steam conversion effected by the heat from the desired product.
ABSTRACT
The production of a hydrogen-containing gas is effected by mixing a hydrocarbon feedstock with steam, a preliminary steam catalytical conversion of the resulting steam-gas mix-ture, followed by a primary catalytical conversion and a secondary steam-oxygen catalytical conversion. The secondary conversion is carried out with the supply of an oxygen-containing gas mixed with a heat-transfer agent in a volume ratio of the heat-transfer agent to oxygen equal to 0.5:30.0 and heated to a temperature of not more than 900°C. The desired product obtained in the secondary conversion is deli-vered to the primary conversion for carrying out the process of a steam conversion effected by the heat from the desired product.
Description
7 ~
`
PROCl~SS FOR PROllUCING HYDROGEN-CON~AINING GAS
~hd pressnt inv~ntion r91ates tD eonvf~rsiDn of ahydrrJ
carbon faedstock and, more particularly, to a prDcass for prDducing a hydrDgen-containing ga9.
~he prasent invention is u93ful in the prDductiDn Df .: .
: ammDnia, mf3thanol, higher alcDhDls and hydrDgen. . -;
~: Known in the art are num3r3us processes fDr the prDduc~
tion Df a hydrDgen-cDntaininggag, ~Dr example, a proce99 ~?~ ~for prDducing a nitrDgen-hydrogen mixture (US, A, 3441393) which comprisf3s preheating of a starting vapDur-hydrocarbDn j mlxture by the heat of cDmbustiDn products, a steam con~
version in the first stage in the presf3nce Df a catalyst ~ ~-~: at a temperature Df frDm 400-540C to 750-850C due t~ the -~
beat Df cDmbusbion product9 at whioh up tD 70% r3f the star~
tin8 hydroearbon feed is reacted, cDnversion in the second ~: stag~ effacted Dn a catalysb with air supply, th~ cDnver- ~ ~:
sion prDducts at the Dutlet from th0 second stag~ of con~
v~rsiDn having bemperatur9 of 920 to 1,050C. .. :~
:~ Known in the art is a proc099 for prDducing a ni~rDgen-- -hydrogen mi~ture (GB, A, 2082623) comprising pr~heating:. .
of bhe sbarting steam-hydrocarbDn mixture by the heat , ., ~ from flue gas0s, a catalytical steam cDnversion in the A~ first:stage wherein up to 20-50~ Df the starting hydrDcarbDn :.
fe~d reacbs and which i9 effected at a temperature of from -~-.. `~
400 tD 650-750C ansured by the heat Df th0 products Df : :
combustiDn Df tha heating gas~ a process Df a catalytical `
~: steam eo~v0rsi~n in tha s0eDnd stage wherein 50 to 2~o Df .-the sbarting hydroearbon feed are reacted and which is .~ ;~
' , ~ , "'~
~,~C,~ id, effeeted at a temperature of o50-750C tD 750-850C due t~
an indireet heat frDm a heat-transfer frDm the prDduets f cDnversiDn Dbtained after bhe third stage of cDnversion n a eatalyst with air supply, the eDnversiDn prDduets after the third cDnversiDn sta~e having temperature Df 920 to 1,050C.
~ his prior art proeess for the prDductiDn of a nitrD~en-hydrDgen mixture as cDmpared tD US, A, 3441393 has advantages residing in a reduction, by 30%, Df the cDn-.
sumptiDn Df natural gas eDnsumed fDr heating, a more ef~feetlve, as eompared tD US, A, 3441393, eDnversiDn in the first stage whieh enables a redueed, by 100-150C, temperature of the prDees~ as eDmpared bD the steam eonversiDn eonditiDns : deseribed in US, A, 3441393. ;.;~
HDwever, in earrying out this prDeess it is necessary : bD use an increased amDunt of a catalyst due tD inefficiency ; of the proeess Df a steam conversiDn in the first stage;
moreDver, there is a pressure drDp between the reaetion ; mi~ture and the cDmbustiDn prDducts, instability ~f the`
.-~ steam eDnversiDn eonditiDns in bhe seeDnd sta~e due to fluc~
:~ tuatiDns of the temperature~ cDnditions of the e4nversion ~` -prDduets at the outIet frDm thethird stage, a consi~
`~ derable rate of consumption Df the hydrDcarbDn feedstDck -~
fDr maintaining temperature Dptimal for the prDcass in the ` : `
first stage o~ cDnversion dua tD an insufficient amDunt `~ ~
~ Df~heat brDught by the current Df prDcess air intD:the ~ ~ -: : third stage Df cDnversiDn. `:~
::,.'"' 2 ~ 2 ~
_ KnDwn in the art is a prDcess fDr prDducing a synthe-sis-gas for the prDductiDn Df ammDnia from hydrDcarbDns (US, A, 4376758) comprisings preheating Df the starting ~ ~:
hydrDcarbDn feed; separatiDn Df the starting steam-hydrocar-bDn mixture inbD two streams cne Df which is subjected tD :~
, .
a steam cDnversion in th~ Pirst staga by the heab of a fuel gas, while in the secDnd stage the prDcess of cDnversiDn is cond.ucted with an excess D~ air tD ~ive a nDn-stDichiomat- :~
ric mixturs fDr the synthesis of ammDnia; the secDnd stream D~ the starting hydrDcarbDn f~ed is subjected tD -~
a steam conversiDn with a d~grae Df 90-95% due bo an in~
direct heat-exchange with a nitrDgen-hydrDgen mixture ob~
tained by mixing the first stream Df the converted gas. . .;
after the second 5tage and the secDnd stream after the`.
procass of steam cDnv~rsiDn0 ~his mixture Df both str3ams `~``. `
has a cDmpDsiti~n suitable fDr the synthesis Df a~mDnia with~ut any further treatment0 ~his prDcess has an advantage Dver that Df US, A, 3441393 in reduction Df the co~sumption Df hydrDcarbDns fDr heating by about 30~0. . `-However, this prDcess features an inefficient use Df a catalyst durlng the steam cDnversioP Df bDth sbraams o~
the steam-hydrDcarbDn iLixture, a considerable cDnsumptiDn of hydr~carbon3 for ha_ting, a gr3at conten`t of inart methane ln th~ nitrDgen-hydrDgen mixture Df the secDnd straam due tD carryinJ DUt the process Df conversion in a . ...
single stage with severe temperature conditions.
~ , , , ,: ' ,~j ~ 2 ~ ~3~ L~ ~
Known in the art i9 a prDc~ss for the prDduction of a synthesis-gas (US, A, 4~331182) comprising the use, in the first stage Df a preliminary adiabatic steam cDnversiDn, Df a steam-hydrocarbDn mixture at a temperature Df 440-510C
to a temperature of 400-500C under a pressure within the range of frDm 1 tD 30 kg/cmC~ the use Df steam refDrming in the secDnd sba~e of the prDcess effected at the accDunt f tbe heat Df the fuel gas at a temperatura Df ~rom 400-500 tD 750-850C and, later on, in the third stage Df cDnversion ~-with air at a tempeiature Df the converted gas at the outlet frDm the third stage Df 920-1?050C. ~his prDcess has an advanbage residing in a ~higher e~ficiency of utilization - ;
f the catalyst of the primary rafDrming which enables its use in a smaller vDlume (the primary conversiDn stage).
However, this process is eff~cted at the stage of a prs~
liminary adiabatic steam cDnversiDn under nDn-Dptimal tempe-rature condition9j especially in t~he case Df u9ing natural gas as ths starting hydrDcarbDn feedstDck which results in a lDwer degree of convsrsion Df msthane in ths starting hydrocarbDn feedstDck and in a grsater volums Df the ca~
talyst smplDysd in the stage Df ths primary cDnversion.~ -KnDwn in the art is~a prDcsss for prDducing a hydrDgsn~
contalning gas (~ , 106076, A) cDmprising mixing of the hydrDcarbDn feed wl~h sbeam, s9paratiDn D~ the c~mmDn flDW ' S;`
into two part9~one of which is subjected ~o the ~lrst stage ,;`~
of a stsam catalytical c~nversion and thsn passed to ths~ ' sscDnd stage of a stsam catalytlcal conversi~n, whersinto æ~2~7~ ~
,, ~
~ -5- ;~
,'d ~, ' '.
''`t~
i the s~ccnd part of the initial steam-hydrocarb~n flow is als~ fed. ~he prDeass Df c~nversiDn in the seeond staga ¦ is ef~ected with the formation of the desired product at a ; -~ temperature within the range o~ ~rDm 920 bD 1jO50C with ¦~ a ~urther use o~ the heat D~ this prDduct for an indirect heating Df said part Df the cDmmon flow of the initial hydrDcarbon feadstoek in the steam-cDnversiDn stage. ~;
~his process envi9ages csrrying-Dut the steam con- - `
version of the hydr~carbDn feedstDck under a pressure within the range of from 25 tD 50 bar and at a temperature at -3~ the beginning of the process ~ from 450 tD 700C at a mass . . ~ ..
ratio of sbeam tD the hy.lr~carbDn equal to 2.5-4.5:1 on a nickel catalyst and at ~80-790C at the end Df the steam conversion. ~ha secDndary cDnversion is earried out while supplying a stream o~ proc9ss air heated to a temperature -~
ran~ing ~rom 700 tD~900C in an amDunt ensuring temperature - `~
o~ ~rom 850 ~D 1,000C at the Dutlet I~r~m the secondary eonverqion stage.
his process makes it pDssible to obtain a hydrogan~
eDntaining gas with a ratiD o~ (H2+C0)/N2=1.9 which is as-socla~ed with a considerable cDnsumption D~ snergy;for eompression of the axeessive air and with a 1DSS Df a pDr- ; `,~
tion of the hydrocarbon feedstDck upon reactiDn w}th Dxygsn D~ said excessive air.
, ., ~ .; ..
' ~
,.. ,.,. i~.. ... . .
~ i ~
2 ~ 2 ~ ~ l L ~
Ib is an Dbjecb of ths present invsntion tD prDvide a 1 prDcess fDr the productiDn of a hydrogsn-cDntaining ga~
a which wDuld make it possible tD lower power con~umptiDn fDr ~ 1ts carrying out and to reduce rates of consumptiDn of the i~ reagents.
j It is anothsr Dbject of th~ present invention tD provide a prDcess for the production of~a hydrogen-c~ntaining gas which wDuld make it possible to reduce cDnsumption ~f the ~
r~eagents for the manufacture of the desired prDduct, whils ~ -ensuring a stabl~ composition of the gas. ~ ~
. .,,,;, hsse Db;jects are accDmplish~d b~y that in a prDcess ~ `~
for the prDductiDn Df a hydrDgen-containing gas cDmprising ,',!,'.'~
mixing Df a hydro:carbo~n fsedstDck with steam, a prsliminary : catalytica1 steam cDnvsr~siDn of bhs resulting m1xture, a pri- -.
.~ mary catalytical stsam cDnvsrsi~on and a subssquènt sscondary sbsam-Dxyesn cabalytical convers1Dn with bhe supp1y Df an : `
~ oxygen-cDntaining gas~th~rs~tD at à temperaburs of:not mDrs ;~ tban 900C to givs bhe desirsd~product, del1vering the latber to the primary;cDnvsrsiDn~to carry Dub a~prDcsss f~a~steam conversiDn by ths~hsat ~rDm the d~=sir=d: product, :
:acci~rding tD the~p~r=~=~nt i~nv=ntiDn,~ ths Dxyg=n-cDnbaining : ; gas~supplied to ths s~condary convsrsion is mixed9 pri~r ~ :;
; to hsating, with a heat-tran~fsr agsnt in a volums ratio `,-., b=tw=sn~th=~hsat-tran=f=r~ae=nt and Dxyesn squa~l to 0.5:30Ø
owin~ to~th= pr===nb inv~ntion it has b~com= possible `~ to r=duca thc rat= Df~DDnsumption Df the oxyeen-containing `~
~ . , .
- æ ~
-7~
gas and, henca, to lower the .rata of alectric power consump-biDn for its prcparation, as well as tD reduce tha rate ~ ~ :
Df the bydrDcarbDns reacting witb the oxygen-containing ~::
gas in the stage Df the secDndary steam-Dxygen converYion.
The total rcduction of bha power consumption, as compared to ths prior art prDcess (EP, 106076, A) i9 aqual tD
0.6 GJ/t NH
In accDrdanca with the present inventiDn, it is advi~
sable to use staam and~Dr carbDn:dioxide as the heat-transfer .~`-``.
agant which is acDnomically afficiant; carbon diDxida also facilitatas shifting o~ the thermDdynamic equilibrium Df the secDndary cDnv~ers1Dn towards the for:matiDn of carbon mDnoxide and lmprovas guality of the~d~esire`d:prDduct intended for tha manuf3ctura of alcohDl characterizà~d by the parametar Df bhe~ratiD H~/C0.
For: sbabLlizatiDn Df the temperature cDnditiDns Df the .
procas= o~ thc primary~cDnver=iDn and, henoa, for ehsuring stabLliby of tha second=ry cDnversi~Dn, it is advi=abl=j :
acoording bo~tb= pre=enb inue~ntiDn,~tD take 0.1-2.0 VDl~
~::`of the oxygsn-cDntainitlg:gas of:it~=:tDtal amount and- mix it with:the desired prDduct,:prior t~o~mixlng; with th= he=t~
tran=fer agenb, priDr to deliver`ing said desired prDduct to the primary cDnversion.
~, o lDwer the~cDn=umption of the oxyg=n-c~nta}ning:gas: :
: in the sacondary cDnversiDn and to~imprDve efficiency DI
the catalyst use, in accDrdance with the present inventiDn ~`it lS =dvisable th=t th= preliminary steam catalytlcal con~
.
7 ~t ~
~ -8-- versiDn bs cDnducted at an initial temparatura D~ 540-570C.
., ~ Further Dbjects and advantages of the present invention ~ ~-.~ will nDw bacDma mora fully apparent frDm tha fDllowing detail~d d~scription of the process for prDducing a hydrDgan~
d containing gas and from sxamples illustrating particular embD-;il diments D~ this prDcess.
~i The procsss fDr prDducing a hydrogen-cDntaining gas according tD tbe presant invention is based Dn tbe msthDd Df ~ : :
~: a twD-stsp steam-Dxygsn catalytical cDnversiDn. `
~he process accDrding tD the present inventiDn is bassd on the uss, as ths starting feedstDck, Df such hydrocarbDn ~ -.
materials as, fDr axample, methans, ethane, prDpans and mixtu-r~ss tbsreDf; bigher hydrDcarbDns which under nDrmal cDndi~
~:~ tiDns are in a gassDus Dr liquid state. .`.-3 ~ In acc~rdancs wlth the procsss of the pressnt invsn~
tiDn said hydrDcarb~n fssdstDck~ prsferably compressed tD a pressure Df fr~m 1 tD 100 bar and having tamperaturs Df ~00C .
: is mixed with 9team in amounts ensuring the ratiD Df H20/C
equal to 2.5-4'1. Ths temperature Df steam in thls case is ~`
equal to 380C. Aft9~ intermixing the resulting gas-steam ~ ~ ;
mlxture has the temperature af~abDut 390C
In accDrdance wi~h the present inventiDn9 the resulting - ;
~` steam-gas mixture is heated tD a temperature within the range~ Df from 48Q t~ 570C, preferably tD 540-570C, and sub~
: jected tD a preliminary st~am catalytical cDnvarsiDn using, ~ : fDr example7 a nickel Dr nickel-c~balt catalystO The prDcess ~. .i : Df the preliminary steam cDnversiDn is adiabatic and e~
. ~
, ' . ' ' -9~
fec~ed ab ths accDunt Df the physical heat of the staam~
gas mixture tD a temperature Df ~rom 440 tD 510C, preferably tD a temperliture o~ from 470 tD 480C. `~
.,~ . .,:
~ he heating Df the starting steam-gas mixture to a tem-perature preferably equal tD 540-570C is e~plainsd by the ;~ i~act that at a tamperaturs belDw 540C under condibiDns of an adiabatic process it is necessary tD usa grsater vDlumes f the catalyst.
he admission, tD tha stage Df the prsliminary steam ~` c~nversiDn, Qf tbe steam-gas mixture at a temparature Df ~i above 570C causas cracking Df higher hydrDcarbons resulting ,. ,,,~,,,;,!.j~ ~ in the formation Df carbDn black.
;~ 3he use, in the preliminary cDnversion, of the steam-gas mixture with a temperature of 540-570C makas It pDs-sibIe tD increase the efficiency of reactin~ Df thà compDnents `~
and to lDwsr, tharsby, the cDnverted ~as tsmperature after ~`
the preliminary cDnversiDn which upDn a f urther primary catalybical conversiDn anebl~es reduction Df cD~nsumpbiDn Df `~ the D}~ygen-cDntaining gas. A hi8her de~;ree of conversion ~ Df the starting hydr~ocarbon-cDntaining I`eedstDck make~ it ;~ pDssible to daliver, to a subsequent prilnary catalytical ; -~
cDnversiDn, a~prDduct -~vith an increased content Df hydrDgen, thus favouring an încreased afficiency Df the emplcyed cata~ ;
3~
lyst~and enabling the use Df smallar volumss of the lajtter~
,3~ After 9aid preliminary conversiDn the partly convarted gas with a tempera~-ure of 440-510C is subjected to a primary steam oatalytical cDnversion by elavating tamperature of the -10~
....
reactiDn gas to 650-850Co The steam cDnversiDn in this case is effected according to an andothermal r~actiDn using a conventiQnal, e.g. nickel, catalyst. The reactiDn gas with ~ -the temperature Df 650-850C is subjected to a secondary steam catalytical cDnvelsi~n in the prasence Df an Dxygen-cDntaining gas. The Dxygen-cDntaining gas supplied to the secondary conv~rsion has a tempbrature o~ not mDre than 900C.
In acc~rdance with the present inventiDn, the Dxygen-cDn-taining ~as is mixed with the heat-transfer agant, priDr tD . `
heating bo said temperature, in a vDlume~ratio bebwesr. bhe heat-transfer agent and o~ygan equal tD 0.5:30Ø
Tbe upper llmi~t (30.0) Df~tbe abDve-speolfi6d vDlume ratio is defined by tbe cDnditiDns of preparation o~ the de- ? ``
sired product intended f~r use in bhe producbiDn~f a~mDnia wh~re`air is us~d as th~ Dxygen-containing gas. In this ca9 the obtained desired product has the stoichiDmetric ratio of H2:N=3 ~ be lDwer~limlt (0.5) Df said vDlume ratiD is defined ~
by the requirement Df a safe character D~ the process exclu-ding break-t~hrough~oP oxygen.
As an inert heat-tra~nsfer agent the oxygen-cDntaining gas incDrporates, for~example, steam, carbDn dlDxlde, nitro~
gen, argon. According tD the present~invention, lt is pre~
ferable~to~use steam and/or càrbD~n diDxide as~the heat~
transfer agent.
owing tD the use o~lsteam, pDwer consumptiDn for oompression of an inerb heat-trans~er agent are rcduced, ; ~
since in this case a lDw-temperature heat can be used and the supply Df the heat-~ransfer agent can be effected by way ~f saturatiDn of the Dxygen~cDntaining gas. Thc US9 `.`.``~, of st~am as bhe haat-transfer agent enables the usa of oxygen heated to 900C in the prDcess, whereas in tha cas0 of ab-sence of the heat-trans~ar a~ent in the reacting zone Df oxygen with the ga9 after the primary cDnversion th3 process is substantially n~n-realizabla due tD a high tamperatura in said zDne. ~he use o-~ carbDn di~xida makes it pDssible tD imprDve the ratio H2/C0 in the deslred prDduct (which is an important indicatDr of the desirad producb quality) in i`
bhe case of the productiDn of a hydrogen-containing gas fDr ~ -`~ the preparatiDn of methanDl and higher alcDhols. `
;~ In accordance with an ambodiment Df the prasent in-vantion, priDr to intermixin~ with said heat-trans~ar agant ~;
bhe D~y~en-containing bas ~ox~en or air) in~n amount o~ 0.1-2.0~o by volume o~ its total amDunt i9 remDved and mixed `~ ^
with bhe desired ~rDduct Dbtained as e rasult o~ the secondary ~ -; oatalytioal converslDn of the reaction gas havlng Its tampe-~ rature within the range of ~rom 950 to 1,050C. ~he major 3~ ~ portiDn of the o~ygen-containing gas aftsr mi~ing thareof wlth tha heat-brans~ar agent is~daliverad tD bhe sccondary c~atalytical conversiDn as it has baen msntiDned hereinabove.
he Dxygan-cDntaining ga9 mixed with the dasirad product is dellvered tD~bhe pri~lary cDnversion ~Dr carrying out the steam cDnversion process by the haab o~ the desired prDduct. -~
~J ~
7 ~
!~ --12--.'~.'-~, ' .
Th~ desired prDduct temperature due to the supply Df tha ~ . .
~ygen-cDntaining gas intD the desired prDduct is maintained `- `:
. ~ . . ~
cDnstant and by 20-30C higher than after ths secDndary - ~ -cDnversiDn. ~he dasirad producb at this temperaburs is fed to the prirnary cDnvarsiDh whersin ib is cDDlsd tD a bemperatura ~- -of frDm 500 tD 700C, prafarably tD 500-600C.
Owing tD the supply DI bhe Dxygen-cDntaining gas int .. ~.. .
the desired product formed in the sec~Dndary cDnversiDn the i ~ ~ temperature cDnditi~ns DI the first-staga conversiDn process `
are stabilized, whereby stability Df DperatiDn and Df th9 - .
'~ ~ process ~f said sacondary conversiDn is ensurad, since the "~
gas compDsibiDn after ths primary cDnversion is stabilized ~ . -ab ths inlet tD tha secDndary conversiDn stage.
~; Ths proc~ss IDr prDducing a hydrDgen-cDntaining ga~
aecDrding to bhe present invsntiDn makes it pDssible bD Dbtain ~: a nitrogen-hydrDgen mixture either dirsctly suibable fDr tha synbhesi3 Df ammDnia, or a nitrogen-hydrDgen mixture of the .
stoichiDmetrie co~np~sition emplDyad in the synthesis ~f amm nia In a low-temperature separation~ ~r recDvery Df excessiva nitrDgen under bhe most effici~nt (~rDm the ecDnDmic stand~
pDint) process conditiDns. FurthermDra, the process accarding tD the present invention makes it pDssible to obtain :a synthe~
sis--gas ~or th~ prod uctiDn cf alcDhDls Df a broad specbrum with an optimal ratlD Df~ H2/CO. ~ha proceas aceDrding to the .
`~ present inventiDn makas it possible tD lDwsr pDwer cDnsumption i n b he pr od uc b i D n Df a mmD nia by 0 . 5-5 . 0%, 7 ~ 3 ~: ~
For a better understanding D~ the present invention, some speci~ic examples illustrating it ` particular embDdi ..
ments arc given herainbelDw. ;.
Example 1 .-Natural gas D~ the ~DllDwing compDsition CH4=92.8%, C2H6_3,9~o~ C7H8=1~1~o~ C4H1o=0~5%, N2=1.6%, C0=0.1% and supplied :;`
under ths pressure of 4~3 MPa was mixad witb staam in ths ratiD D~ st~am:hydrocarbDn =3:1, heated to the tamperatur~
o~ 570C and supplied to the stage of the primary steam conversion~ where~rDm it was withdrawn at the temperature -~
of' 713C and with the content Df CH4 in the dry cDnverted gas Df 26.6%; the degree Df cDnversion of metbans at the sbage of the primar~ conversion being ~qual to 32~o~ ~he con~
verted gas a~ter the stage of the prlmary steam conv~rsion ;~
was fed to the stage of the secondary steam-oxygen cDnvarsion. ~ :
Also ~ed thereto was a steam-air mlxture heated to the tem-perature Df 900'C with the ratio o~ H20/02=0.5.
~he desired product temperature at the outlet of the .
qecondary steam-oxygen cDnversion stage was 970C, the cDntent o~ methane - 0.53% and the ratio (H2+C0)/N2=2.08. A~ter the tage of the secondary conversion the dasired product was delivered to the stage o~ the primary conversion, wherein it was cDoled to the temperature o~ 620C giving its heat .~
to the endothermal steam conversion of methane Dccurring at ::
this stage.
xample 2 :.
Natural gas o~ th0 following composition: CH4=92.8%, J ' , .~:
.:,.: .'- :, , :~ ' ' :~',',.~ ' ' ,, , ,'~,,.',i: ': ~' . .
` l 2 ~ 7 ~
~ -14~
;~ ~
2 6 3 9%~ C3H8 1.1%, C4H1~=0-5~o~ N2=1 6%~ C2- 1% und~
th~. pressure of 4.3 MPa was mixed with sbeam in bhe rabiD
Df 3.5:1, heated to the bempsratiure of 570C and supplied . .,".
tD the sbags of the primary steam cDnversion, where~rDm :-,.',,.. :'.. ~' ib was wibhdrawn at the temperature Df 840C and with '-'-.'.
the cDntent of metihane Df 9.0~0, bhs degree Df cDnversiDn ',':"~''', f m=thane at the stage Df the yrimary cDnvsrsiDn being 57~0. ,.,.
he cDnverted gas after bhe sbage Df the primary steam con~
version was supplied tD the stage of the secondary steam- ~`
oxygen conver9iDn. Al90 fed bD thi9 stage was a 5team-air mix- :.. ~
ture~with the ratio of.H20/02 ~ 30 and with the temperature ;~ ~ `
of 800C. ~he desired producb temperaturs at the outlet from . ,~.
the stage of~the secondary steam-oxygen conversion was 940C. ''-' .,' The ratio of (H2~C0?/N2=3.1. After the stage of bhe secon- ' '''' dary conversion the dssired product was delivered bo bhe ., :;.' `.
stage of the primary s,beam,conversion, wherein ib was cooled .. ~`
to the temperature Df 620C giving its heab to the endDther- ,, .',.
mal conversion Df mstbane Dccurring at bhis sba~e.
Example 3 ~ '."',.
A mixtur~ of propane and butane in bhe ratio Df 2:1 res- ,'.'~.. '.
pectively under the pressure of 8.0 MPa was mixed wit~ steam in the ratio of H20/C _3:1 and was supplied, at the tiempe~
rature o~ 500C, tD the stags Df bhe primary sbeam conversiDn, wherefrom it was withdrawn at the ttemperature of 826C .'~
wlth the cDntenb Df meth9ne Df 17.8%.~he aDnvertad gas after '','~
the stage Df bhe primary steam:cDnversion was supplied tD the ,'.~.~.', sta~e of bhe secondary sbeAm-oxy~en conver~ion. Al90 fed to .... : -j'`; l ` ` : :
!"~
! I
2 ~ 7 4 ~
this stage was an Dx~/gen-hydrDcarb~n mixture h~ated tD the temperaturs of 5~0C and having the ratiD of C02/02=6:1. `:; ;.
How0v0r, insignificant fluctuations Df th~ paramet~rs of the :.
prDcscs str~ams result~d in vari.atiDns of tamp9raturs aft~r the s=cDndary cDnv~rsiDn frDm 970 tD 950C, while the con-tsnb o~ residual m~thane changed frDm 0.49 to 0. 70%. At va~
riations Df the desired product bemperature aftdr the sccon~
dary conversiDn from 970 to 950C the content D~ residual ~-msthans and tempsrature after ths primary steam aonversion ~ -changed: frDm 17.8 to 19.7% of CH4, while temperatur0 chang~d from 826 to 810C~ In thus cass, when an DxyOen~containing ~.
mixture after th= =t=8e of the secDndary stsam conversiDn ~ .
was supplied into the desirsd product in an amount Df from : ~;
0.1 to 9.0% by volume, the temp9rature prior tD the prlmary cDnv~rsion and, hencs, th3 cDmposition after tha:~
primary cDnv~rsiDn .~f~uld bs 9tabiliz0d. ``
An avsrag0 temp~r~tur= Df bh~ de=ir9d product priDr tD
the introductiDn thsrslnto of a~:smaller portlon o~ the oxyg~n-Gontainlng gas wa~= 960C and, 3ftsr th9 admission, 970C. ~h~ cDntsnt Df resid~u=l:m=thans in the d=sir0d ~ :
product was~0.5% by volume.~After th= stage Df th~ se`condary cDnv~rsion th~ desirsd prDduct was deiivered tD~th= stags Df :
th=~prlmary st=am co~nver=lon, wh~rcin it was.coDled to the tempsrabure of 570C:giving its h0at to tha ~ndDbhsrmal steam conv~rsion of methan0 occurri ng a t this stag=. ~ -;
.~ ~"'' ,., i,: , , , ~, -. "~-: . ,-:, .:. :. ., , ,: , , . ~ . :
, ~:,., ' - . . .- : ~ : . .
. , ,,~,," ~, ,;, ., , . . . . . . , ~ , .
r"S . ', :
~ -16-~: . '', -,'.
Exa mp l s 4 . . .
Natural gas D~ the fDllDwing compDsitiDn: CH4=92.8%, ~;
2 6 3 ~ 9Yo~ C3Hg-1. 1%~ C4H10=Oo 5%~ N2=1- ~a~ C02=0- 1% und~r the prassure of 4~3 ~a was mixed with steam in the ratiD
of stsam tD hydrocarbon -3:1, heatsd to the temperatur9 570C and fed tD the st`age D:~ an adiabatic preliminary ~-conversiDn, whersin at the account Df a physical heab Df the steam-gas mixture thare Dccurrad a prDcess Df a steam conversiDn with cDoling Df the reactiDn mixture tD the t~m~
perabure Df 490QC. The gas after the praliminary cDnversiDn had the fDllDWillg CDlllpDSitiDtl: C0=0~07~o~ C02=2-50%~ H2=9.32%~
CH = 22.21%, H20 = 65~o by vDlume, N2=0.90%. ~`
he ga9 aftsr the praliminary conversion was delivared ~ `
tD the stags Df the primary steam convarsion, wharefrom it `~ ~`
was withdrawn at the temp~laturs Df 754C and with the con-tent of CH4 in the dry converted gas equal to 21.20~o. The cDnverted gas after the 9tage Df the primary steam cDnversion was d~liverad to the stage Df the secDndary steam-oxygen cDnversiDn. Fed to the same stage was alSD a steam-air mix- ;~
tura heatad to the~temp~rature Df 500C and havlng the H20/02 ratio 0qual tD 0.5.~The de9ired prDduct t~mparature ~
at the outlet from tha secDndary 9team ~x,ygen cDnvsrsiDn ~ ~`
``~ `stage~ was 970C, tha cDntent of msthane ~,las 0.5~0~and th~
ratlo ~H2+C0)~/N2=2.08. After ths stage of tne secDndary conversion the desired product was delivered to the~stag~
of tha~primarg 9team cDrlversiDn, wherein it wa9 coDled bo the tempsrature Dfi 540C giving its heat bD the endothermal r steam conversiDn Df msthane.
~ . ,, ,.. .. . ~. :. : . : . :
2 !~ 2 ~ 7 4 ~
~ Example 5 .``~ The starting steam-hydrocarbQn mixture of ~xample 4 ~; was heated tD tha t3mp~raturs of 540C and deliv3red to tha ~stage Df an adiabatic prsliminary conversion, whsrain a~ ~-prDcess of stsam cQnvsrsion with cDoling zf the reacting mix~
tur~ tD the tsmp~raturs o~ 470C Dccurred due tD a physica~
; b~at Df the vapDur-gas mixtura. Ths temparatur~ of preh~3ting f ths stsam-air mixture witb the ratiD of H20/02=0.5 was~
600C. The temperature Df tb~desirad prDduct aftex coDling : `
3 at ths sta~e Df the primary conversi~n was 540C and ths ratio of (H2+C0)/N2=2.08. ;~ :
xample 6 `~
Nabural gas of tbe fDllDwiDg CDmpDsition CH4-92.8%, 2 6 3 9%~ C3H8~ %~ C4H1O=-5%~ N2=1 ~ 6~0~ CO _ OD 1YO under bhe pressurs Df 4.3 MPa was mixsd wit.~ sbsam in the ratio of steam to ths~hydrDcarbon of 4:1, hsated tD the tampsrature :.-~; : D~ 570C and supplied tD the stage:Df an adiabatic~preliminary :~ cDnversion, whare1n at the~accDun~b~Df a physical haat frDm ths steam-gas mixture a~process of steam converslDn tDok place with coDling of the rsact~ing mixture to th~ tempsratur3 of 485C. ~h~ ga:s after the preliminary cDnversiDn had the : fDllDwing composition: C0 = 0.05yo~ C02=2.35~o1 H2=8.86%, ~;:
CH =: 17 . 55~0~ N2=0.69~o~H20 =70,5%.~he gas after the prelimi~
nary cDnversiDn was deliver:ed~ bo tb~ stage Df th~ primary ;~ `
st:eam cOnverslon, wbarefrom it was withdrawn at the bempera~
t~ure Df 760C and with bh9 oDntent of CH4=15.38~0 in the dry converted gas. The cDnvertsd gas after the stag~ of the , :
2~2~7~
.
' ! -18-~,, . ~.
primary conv~rsiDn was deliver~d to the stage of the secon-dary steam-o~ygen conversion. A1SD fed tD this stage was ;~
- a stsam-Dx~g~n-nitrDgen mixture heated to the temperature ~-f 750C with tha ratio o~ (N2+H20)/02=5.47, the ratiD o~
H20/02 bein~ equal bo 0.59. In the case o~ availability ;1 o~ nitrDgen under pres~ure, it was used as an additive ~-~
to thc prDcess air. ~he desired producb tamperature at - ~`
tba outlet from the stage o~ th~ sacDndary sbeam-oxygen-nit-rogen conversiD~ was 940C, the content of methane - 0.~%, -1~ the ratio Df (H2+C0)/N2 = 2.08.
t~ A~ter thc stage of the secondary conversion the desir=d product was delivered to the stage of the primary steam con-v=rsion, wber=in It wa= cooled to the temperaturs of 540~C, ;~
;~ ~ giving it= beat tD bhe endotbermal sbeam conversiDn Df me-tbane.
' ',',' ,'. ,;
,~ ,.',,.'. ,,`
` ~ ; ' ,,j~",.,",
`
PROCl~SS FOR PROllUCING HYDROGEN-CON~AINING GAS
~hd pressnt inv~ntion r91ates tD eonvf~rsiDn of ahydrrJ
carbon faedstock and, more particularly, to a prDcass for prDducing a hydrDgen-containing ga9.
~he prasent invention is u93ful in the prDductiDn Df .: .
: ammDnia, mf3thanol, higher alcDhDls and hydrDgen. . -;
~: Known in the art are num3r3us processes fDr the prDduc~
tion Df a hydrDgen-cDntaininggag, ~Dr example, a proce99 ~?~ ~for prDducing a nitrDgen-hydrogen mixture (US, A, 3441393) which comprisf3s preheating of a starting vapDur-hydrocarbDn j mlxture by the heat of cDmbustiDn products, a steam con~
version in the first stage in the presf3nce Df a catalyst ~ ~-~: at a temperature Df frDm 400-540C to 750-850C due t~ the -~
beat Df cDmbusbion product9 at whioh up tD 70% r3f the star~
tin8 hydroearbon feed is reacted, cDnversion in the second ~: stag~ effacted Dn a catalysb with air supply, th~ cDnver- ~ ~:
sion prDducts at the Dutlet from th0 second stag~ of con~
v~rsiDn having bemperatur9 of 920 to 1,050C. .. :~
:~ Known in the art is a proc099 for prDducing a ni~rDgen-- -hydrogen mi~ture (GB, A, 2082623) comprising pr~heating:. .
of bhe sbarting steam-hydrocarbDn mixture by the heat , ., ~ from flue gas0s, a catalytical steam cDnversion in the A~ first:stage wherein up to 20-50~ Df the starting hydrDcarbDn :.
fe~d reacbs and which i9 effected at a temperature of from -~-.. `~
400 tD 650-750C ansured by the heat Df th0 products Df : :
combustiDn Df tha heating gas~ a process Df a catalytical `
~: steam eo~v0rsi~n in tha s0eDnd stage wherein 50 to 2~o Df .-the sbarting hydroearbon feed are reacted and which is .~ ;~
' , ~ , "'~
~,~C,~ id, effeeted at a temperature of o50-750C tD 750-850C due t~
an indireet heat frDm a heat-transfer frDm the prDduets f cDnversiDn Dbtained after bhe third stage of cDnversion n a eatalyst with air supply, the eDnversiDn prDduets after the third cDnversiDn sta~e having temperature Df 920 to 1,050C.
~ his prior art proeess for the prDductiDn of a nitrD~en-hydrDgen mixture as cDmpared tD US, A, 3441393 has advantages residing in a reduction, by 30%, Df the cDn-.
sumptiDn Df natural gas eDnsumed fDr heating, a more ef~feetlve, as eompared tD US, A, 3441393, eDnversiDn in the first stage whieh enables a redueed, by 100-150C, temperature of the prDees~ as eDmpared bD the steam eonversiDn eonditiDns : deseribed in US, A, 3441393. ;.;~
HDwever, in earrying out this prDeess it is necessary : bD use an increased amDunt of a catalyst due tD inefficiency ; of the proeess Df a steam conversiDn in the first stage;
moreDver, there is a pressure drDp between the reaetion ; mi~ture and the cDmbustiDn prDducts, instability ~f the`
.-~ steam eDnversiDn eonditiDns in bhe seeDnd sta~e due to fluc~
:~ tuatiDns of the temperature~ cDnditions of the e4nversion ~` -prDduets at the outIet frDm thethird stage, a consi~
`~ derable rate of consumption Df the hydrDcarbDn feedstDck -~
fDr maintaining temperature Dptimal for the prDcass in the ` : `
first stage o~ cDnversion dua tD an insufficient amDunt `~ ~
~ Df~heat brDught by the current Df prDcess air intD:the ~ ~ -: : third stage Df cDnversiDn. `:~
::,.'"' 2 ~ 2 ~
_ KnDwn in the art is a prDcess fDr prDducing a synthe-sis-gas for the prDductiDn Df ammDnia from hydrDcarbDns (US, A, 4376758) comprisings preheating Df the starting ~ ~:
hydrDcarbDn feed; separatiDn Df the starting steam-hydrocar-bDn mixture inbD two streams cne Df which is subjected tD :~
, .
a steam cDnversion in th~ Pirst staga by the heab of a fuel gas, while in the secDnd stage the prDcess of cDnversiDn is cond.ucted with an excess D~ air tD ~ive a nDn-stDichiomat- :~
ric mixturs fDr the synthesis of ammDnia; the secDnd stream D~ the starting hydrDcarbDn f~ed is subjected tD -~
a steam conversiDn with a d~grae Df 90-95% due bo an in~
direct heat-exchange with a nitrDgen-hydrDgen mixture ob~
tained by mixing the first stream Df the converted gas. . .;
after the second 5tage and the secDnd stream after the`.
procass of steam cDnv~rsiDn0 ~his mixture Df both str3ams `~``. `
has a cDmpDsiti~n suitable fDr the synthesis Df a~mDnia with~ut any further treatment0 ~his prDcess has an advantage Dver that Df US, A, 3441393 in reduction Df the co~sumption Df hydrDcarbDns fDr heating by about 30~0. . `-However, this prDcess features an inefficient use Df a catalyst durlng the steam cDnversioP Df bDth sbraams o~
the steam-hydrDcarbDn iLixture, a considerable cDnsumptiDn of hydr~carbon3 for ha_ting, a gr3at conten`t of inart methane ln th~ nitrDgen-hydrDgen mixture Df the secDnd straam due tD carryinJ DUt the process Df conversion in a . ...
single stage with severe temperature conditions.
~ , , , ,: ' ,~j ~ 2 ~ ~3~ L~ ~
Known in the art i9 a prDc~ss for the prDduction of a synthesis-gas (US, A, 4~331182) comprising the use, in the first stage Df a preliminary adiabatic steam cDnversiDn, Df a steam-hydrocarbDn mixture at a temperature Df 440-510C
to a temperature of 400-500C under a pressure within the range of frDm 1 tD 30 kg/cmC~ the use Df steam refDrming in the secDnd sba~e of the prDcess effected at the accDunt f tbe heat Df the fuel gas at a temperatura Df ~rom 400-500 tD 750-850C and, later on, in the third stage Df cDnversion ~-with air at a tempeiature Df the converted gas at the outlet frDm the third stage Df 920-1?050C. ~his prDcess has an advanbage residing in a ~higher e~ficiency of utilization - ;
f the catalyst of the primary rafDrming which enables its use in a smaller vDlume (the primary conversiDn stage).
However, this process is eff~cted at the stage of a prs~
liminary adiabatic steam cDnversiDn under nDn-Dptimal tempe-rature condition9j especially in t~he case Df u9ing natural gas as ths starting hydrDcarbDn feedstDck which results in a lDwer degree of convsrsion Df msthane in ths starting hydrocarbDn feedstDck and in a grsater volums Df the ca~
talyst smplDysd in the stage Df ths primary cDnversion.~ -KnDwn in the art is~a prDcsss for prDducing a hydrDgsn~
contalning gas (~ , 106076, A) cDmprising mixing of the hydrDcarbDn feed wl~h sbeam, s9paratiDn D~ the c~mmDn flDW ' S;`
into two part9~one of which is subjected ~o the ~lrst stage ,;`~
of a stsam catalytical c~nversion and thsn passed to ths~ ' sscDnd stage of a stsam catalytlcal conversi~n, whersinto æ~2~7~ ~
,, ~
~ -5- ;~
,'d ~, ' '.
''`t~
i the s~ccnd part of the initial steam-hydrocarb~n flow is als~ fed. ~he prDeass Df c~nversiDn in the seeond staga ¦ is ef~ected with the formation of the desired product at a ; -~ temperature within the range o~ ~rDm 920 bD 1jO50C with ¦~ a ~urther use o~ the heat D~ this prDduct for an indirect heating Df said part Df the cDmmon flow of the initial hydrDcarbon feadstoek in the steam-cDnversiDn stage. ~;
~his process envi9ages csrrying-Dut the steam con- - `
version of the hydr~carbDn feedstDck under a pressure within the range of from 25 tD 50 bar and at a temperature at -3~ the beginning of the process ~ from 450 tD 700C at a mass . . ~ ..
ratio of sbeam tD the hy.lr~carbDn equal to 2.5-4.5:1 on a nickel catalyst and at ~80-790C at the end Df the steam conversion. ~ha secDndary cDnversion is earried out while supplying a stream o~ proc9ss air heated to a temperature -~
ran~ing ~rom 700 tD~900C in an amDunt ensuring temperature - `~
o~ ~rom 850 ~D 1,000C at the Dutlet I~r~m the secondary eonverqion stage.
his process makes it pDssible to obtain a hydrogan~
eDntaining gas with a ratiD o~ (H2+C0)/N2=1.9 which is as-socla~ed with a considerable cDnsumption D~ snergy;for eompression of the axeessive air and with a 1DSS Df a pDr- ; `,~
tion of the hydrocarbon feedstDck upon reactiDn w}th Dxygsn D~ said excessive air.
, ., ~ .; ..
' ~
,.. ,.,. i~.. ... . .
~ i ~
2 ~ 2 ~ ~ l L ~
Ib is an Dbjecb of ths present invsntion tD prDvide a 1 prDcess fDr the productiDn of a hydrogsn-cDntaining ga~
a which wDuld make it possible tD lower power con~umptiDn fDr ~ 1ts carrying out and to reduce rates of consumptiDn of the i~ reagents.
j It is anothsr Dbject of th~ present invention tD provide a prDcess for the production of~a hydrogen-c~ntaining gas which wDuld make it possible to reduce cDnsumption ~f the ~
r~eagents for the manufacture of the desired prDduct, whils ~ -ensuring a stabl~ composition of the gas. ~ ~
. .,,,;, hsse Db;jects are accDmplish~d b~y that in a prDcess ~ `~
for the prDductiDn Df a hydrDgen-containing gas cDmprising ,',!,'.'~
mixing Df a hydro:carbo~n fsedstDck with steam, a prsliminary : catalytica1 steam cDnvsr~siDn of bhs resulting m1xture, a pri- -.
.~ mary catalytical stsam cDnvsrsi~on and a subssquènt sscondary sbsam-Dxyesn cabalytical convers1Dn with bhe supp1y Df an : `
~ oxygen-cDntaining gas~th~rs~tD at à temperaburs of:not mDrs ;~ tban 900C to givs bhe desirsd~product, del1vering the latber to the primary;cDnvsrsiDn~to carry Dub a~prDcsss f~a~steam conversiDn by ths~hsat ~rDm the d~=sir=d: product, :
:acci~rding tD the~p~r=~=~nt i~nv=ntiDn,~ ths Dxyg=n-cDnbaining : ; gas~supplied to ths s~condary convsrsion is mixed9 pri~r ~ :;
; to hsating, with a heat-tran~fsr agsnt in a volums ratio `,-., b=tw=sn~th=~hsat-tran=f=r~ae=nt and Dxyesn squa~l to 0.5:30Ø
owin~ to~th= pr===nb inv~ntion it has b~com= possible `~ to r=duca thc rat= Df~DDnsumption Df the oxyeen-containing `~
~ . , .
- æ ~
-7~
gas and, henca, to lower the .rata of alectric power consump-biDn for its prcparation, as well as tD reduce tha rate ~ ~ :
Df the bydrDcarbDns reacting witb the oxygen-containing ~::
gas in the stage Df the secDndary steam-Dxygen converYion.
The total rcduction of bha power consumption, as compared to ths prior art prDcess (EP, 106076, A) i9 aqual tD
0.6 GJ/t NH
In accDrdanca with the present inventiDn, it is advi~
sable to use staam and~Dr carbDn:dioxide as the heat-transfer .~`-``.
agant which is acDnomically afficiant; carbon diDxida also facilitatas shifting o~ the thermDdynamic equilibrium Df the secDndary cDnv~ers1Dn towards the for:matiDn of carbon mDnoxide and lmprovas guality of the~d~esire`d:prDduct intended for tha manuf3ctura of alcohDl characterizà~d by the parametar Df bhe~ratiD H~/C0.
For: sbabLlizatiDn Df the temperature cDnditiDns Df the .
procas= o~ thc primary~cDnver=iDn and, henoa, for ehsuring stabLliby of tha second=ry cDnversi~Dn, it is advi=abl=j :
acoording bo~tb= pre=enb inue~ntiDn,~tD take 0.1-2.0 VDl~
~::`of the oxygsn-cDntainitlg:gas of:it~=:tDtal amount and- mix it with:the desired prDduct,:prior t~o~mixlng; with th= he=t~
tran=fer agenb, priDr to deliver`ing said desired prDduct to the primary cDnversion.
~, o lDwer the~cDn=umption of the oxyg=n-c~nta}ning:gas: :
: in the sacondary cDnversiDn and to~imprDve efficiency DI
the catalyst use, in accDrdance with the present inventiDn ~`it lS =dvisable th=t th= preliminary steam catalytlcal con~
.
7 ~t ~
~ -8-- versiDn bs cDnducted at an initial temparatura D~ 540-570C.
., ~ Further Dbjects and advantages of the present invention ~ ~-.~ will nDw bacDma mora fully apparent frDm tha fDllowing detail~d d~scription of the process for prDducing a hydrDgan~
d containing gas and from sxamples illustrating particular embD-;il diments D~ this prDcess.
~i The procsss fDr prDducing a hydrogen-cDntaining gas according tD tbe presant invention is based Dn tbe msthDd Df ~ : :
~: a twD-stsp steam-Dxygsn catalytical cDnversiDn. `
~he process accDrding tD the present inventiDn is bassd on the uss, as ths starting feedstDck, Df such hydrocarbDn ~ -.
materials as, fDr axample, methans, ethane, prDpans and mixtu-r~ss tbsreDf; bigher hydrDcarbDns which under nDrmal cDndi~
~:~ tiDns are in a gassDus Dr liquid state. .`.-3 ~ In acc~rdancs wlth the procsss of the pressnt invsn~
tiDn said hydrDcarb~n fssdstDck~ prsferably compressed tD a pressure Df fr~m 1 tD 100 bar and having tamperaturs Df ~00C .
: is mixed with 9team in amounts ensuring the ratiD Df H20/C
equal to 2.5-4'1. Ths temperature Df steam in thls case is ~`
equal to 380C. Aft9~ intermixing the resulting gas-steam ~ ~ ;
mlxture has the temperature af~abDut 390C
In accDrdance wi~h the present inventiDn9 the resulting - ;
~` steam-gas mixture is heated tD a temperature within the range~ Df from 48Q t~ 570C, preferably tD 540-570C, and sub~
: jected tD a preliminary st~am catalytical cDnvarsiDn using, ~ : fDr example7 a nickel Dr nickel-c~balt catalystO The prDcess ~. .i : Df the preliminary steam cDnversiDn is adiabatic and e~
. ~
, ' . ' ' -9~
fec~ed ab ths accDunt Df the physical heat of the staam~
gas mixture tD a temperature Df ~rom 440 tD 510C, preferably tD a temperliture o~ from 470 tD 480C. `~
.,~ . .,:
~ he heating Df the starting steam-gas mixture to a tem-perature preferably equal tD 540-570C is e~plainsd by the ;~ i~act that at a tamperaturs belDw 540C under condibiDns of an adiabatic process it is necessary tD usa grsater vDlumes f the catalyst.
he admission, tD tha stage Df the prsliminary steam ~` c~nversiDn, Qf tbe steam-gas mixture at a temparature Df ~i above 570C causas cracking Df higher hydrDcarbons resulting ,. ,,,~,,,;,!.j~ ~ in the formation Df carbDn black.
;~ 3he use, in the preliminary cDnversion, of the steam-gas mixture with a temperature of 540-570C makas It pDs-sibIe tD increase the efficiency of reactin~ Df thà compDnents `~
and to lDwsr, tharsby, the cDnverted ~as tsmperature after ~`
the preliminary cDnversiDn which upDn a f urther primary catalybical conversiDn anebl~es reduction Df cD~nsumpbiDn Df `~ the D}~ygen-cDntaining gas. A hi8her de~;ree of conversion ~ Df the starting hydr~ocarbon-cDntaining I`eedstDck make~ it ;~ pDssible to daliver, to a subsequent prilnary catalytical ; -~
cDnversiDn, a~prDduct -~vith an increased content Df hydrDgen, thus favouring an încreased afficiency Df the emplcyed cata~ ;
3~
lyst~and enabling the use Df smallar volumss of the lajtter~
,3~ After 9aid preliminary conversiDn the partly convarted gas with a tempera~-ure of 440-510C is subjected to a primary steam oatalytical cDnversion by elavating tamperature of the -10~
....
reactiDn gas to 650-850Co The steam cDnversiDn in this case is effected according to an andothermal r~actiDn using a conventiQnal, e.g. nickel, catalyst. The reactiDn gas with ~ -the temperature Df 650-850C is subjected to a secondary steam catalytical cDnvelsi~n in the prasence Df an Dxygen-cDntaining gas. The Dxygen-cDntaining gas supplied to the secondary conv~rsion has a tempbrature o~ not mDre than 900C.
In acc~rdance with the present inventiDn, the Dxygen-cDn-taining ~as is mixed with the heat-transfer agant, priDr tD . `
heating bo said temperature, in a vDlume~ratio bebwesr. bhe heat-transfer agent and o~ygan equal tD 0.5:30Ø
Tbe upper llmi~t (30.0) Df~tbe abDve-speolfi6d vDlume ratio is defined by tbe cDnditiDns of preparation o~ the de- ? ``
sired product intended f~r use in bhe producbiDn~f a~mDnia wh~re`air is us~d as th~ Dxygen-containing gas. In this ca9 the obtained desired product has the stoichiDmetric ratio of H2:N=3 ~ be lDwer~limlt (0.5) Df said vDlume ratiD is defined ~
by the requirement Df a safe character D~ the process exclu-ding break-t~hrough~oP oxygen.
As an inert heat-tra~nsfer agent the oxygen-cDntaining gas incDrporates, for~example, steam, carbDn dlDxlde, nitro~
gen, argon. According tD the present~invention, lt is pre~
ferable~to~use steam and/or càrbD~n diDxide as~the heat~
transfer agent.
owing tD the use o~lsteam, pDwer consumptiDn for oompression of an inerb heat-trans~er agent are rcduced, ; ~
since in this case a lDw-temperature heat can be used and the supply Df the heat-~ransfer agent can be effected by way ~f saturatiDn of the Dxygen~cDntaining gas. Thc US9 `.`.``~, of st~am as bhe haat-transfer agent enables the usa of oxygen heated to 900C in the prDcess, whereas in tha cas0 of ab-sence of the heat-trans~ar a~ent in the reacting zone Df oxygen with the ga9 after the primary cDnversion th3 process is substantially n~n-realizabla due tD a high tamperatura in said zDne. ~he use o-~ carbDn di~xida makes it pDssible tD imprDve the ratio H2/C0 in the deslred prDduct (which is an important indicatDr of the desirad producb quality) in i`
bhe case of the productiDn of a hydrogen-containing gas fDr ~ -`~ the preparatiDn of methanDl and higher alcDhols. `
;~ In accordance with an ambodiment Df the prasent in-vantion, priDr to intermixin~ with said heat-trans~ar agant ~;
bhe D~y~en-containing bas ~ox~en or air) in~n amount o~ 0.1-2.0~o by volume o~ its total amDunt i9 remDved and mixed `~ ^
with bhe desired ~rDduct Dbtained as e rasult o~ the secondary ~ -; oatalytioal converslDn of the reaction gas havlng Its tampe-~ rature within the range of ~rom 950 to 1,050C. ~he major 3~ ~ portiDn of the o~ygen-containing gas aftsr mi~ing thareof wlth tha heat-brans~ar agent is~daliverad tD bhe sccondary c~atalytical conversiDn as it has baen msntiDned hereinabove.
he Dxygan-cDntaining ga9 mixed with the dasirad product is dellvered tD~bhe pri~lary cDnversion ~Dr carrying out the steam cDnversion process by the haab o~ the desired prDduct. -~
~J ~
7 ~
!~ --12--.'~.'-~, ' .
Th~ desired prDduct temperature due to the supply Df tha ~ . .
~ygen-cDntaining gas intD the desired prDduct is maintained `- `:
. ~ . . ~
cDnstant and by 20-30C higher than after ths secDndary - ~ -cDnversiDn. ~he dasirad producb at this temperaburs is fed to the prirnary cDnvarsiDh whersin ib is cDDlsd tD a bemperatura ~- -of frDm 500 tD 700C, prafarably tD 500-600C.
Owing tD the supply DI bhe Dxygen-cDntaining gas int .. ~.. .
the desired product formed in the sec~Dndary cDnversiDn the i ~ ~ temperature cDnditi~ns DI the first-staga conversiDn process `
are stabilized, whereby stability Df DperatiDn and Df th9 - .
'~ ~ process ~f said sacondary conversiDn is ensurad, since the "~
gas compDsibiDn after ths primary cDnversion is stabilized ~ . -ab ths inlet tD tha secDndary conversiDn stage.
~; Ths proc~ss IDr prDducing a hydrDgen-cDntaining ga~
aecDrding to bhe present invsntiDn makes it pDssible bD Dbtain ~: a nitrogen-hydrDgen mixture either dirsctly suibable fDr tha synbhesi3 Df ammDnia, or a nitrogen-hydrDgen mixture of the .
stoichiDmetrie co~np~sition emplDyad in the synthesis ~f amm nia In a low-temperature separation~ ~r recDvery Df excessiva nitrDgen under bhe most effici~nt (~rDm the ecDnDmic stand~
pDint) process conditiDns. FurthermDra, the process accarding tD the present invention makes it pDssible to obtain :a synthe~
sis--gas ~or th~ prod uctiDn cf alcDhDls Df a broad specbrum with an optimal ratlD Df~ H2/CO. ~ha proceas aceDrding to the .
`~ present inventiDn makas it possible tD lDwsr pDwer cDnsumption i n b he pr od uc b i D n Df a mmD nia by 0 . 5-5 . 0%, 7 ~ 3 ~: ~
For a better understanding D~ the present invention, some speci~ic examples illustrating it ` particular embDdi ..
ments arc given herainbelDw. ;.
Example 1 .-Natural gas D~ the ~DllDwing compDsition CH4=92.8%, C2H6_3,9~o~ C7H8=1~1~o~ C4H1o=0~5%, N2=1.6%, C0=0.1% and supplied :;`
under ths pressure of 4~3 MPa was mixad witb staam in ths ratiD D~ st~am:hydrocarbDn =3:1, heated to the tamperatur~
o~ 570C and supplied to the stage of the primary steam conversion~ where~rDm it was withdrawn at the temperature -~
of' 713C and with the content Df CH4 in the dry cDnverted gas Df 26.6%; the degree Df cDnversion of metbans at the sbage of the primar~ conversion being ~qual to 32~o~ ~he con~
verted gas a~ter the stage of the prlmary steam conv~rsion ;~
was fed to the stage of the secondary steam-oxygen cDnvarsion. ~ :
Also ~ed thereto was a steam-air mlxture heated to the tem-perature Df 900'C with the ratio o~ H20/02=0.5.
~he desired product temperature at the outlet of the .
qecondary steam-oxygen cDnversion stage was 970C, the cDntent o~ methane - 0.53% and the ratio (H2+C0)/N2=2.08. A~ter the tage of the secondary conversion the dasired product was delivered to the stage o~ the primary conversion, wherein it was cDoled to the temperature o~ 620C giving its heat .~
to the endothermal steam conversion of methane Dccurring at ::
this stage.
xample 2 :.
Natural gas o~ th0 following composition: CH4=92.8%, J ' , .~:
.:,.: .'- :, , :~ ' ' :~',',.~ ' ' ,, , ,'~,,.',i: ': ~' . .
` l 2 ~ 7 ~
~ -14~
;~ ~
2 6 3 9%~ C3H8 1.1%, C4H1~=0-5~o~ N2=1 6%~ C2- 1% und~
th~. pressure of 4.3 MPa was mixed with sbeam in bhe rabiD
Df 3.5:1, heated to the bempsratiure of 570C and supplied . .,".
tD the sbags of the primary steam cDnversion, where~rDm :-,.',,.. :'.. ~' ib was wibhdrawn at the temperature Df 840C and with '-'-.'.
the cDntent of metihane Df 9.0~0, bhs degree Df cDnversiDn ',':"~''', f m=thane at the stage Df the yrimary cDnvsrsiDn being 57~0. ,.,.
he cDnverted gas after bhe sbage Df the primary steam con~
version was supplied tD the stage of the secondary steam- ~`
oxygen conver9iDn. Al90 fed bD thi9 stage was a 5team-air mix- :.. ~
ture~with the ratio of.H20/02 ~ 30 and with the temperature ;~ ~ `
of 800C. ~he desired producb temperaturs at the outlet from . ,~.
the stage of~the secondary steam-oxygen conversion was 940C. ''-' .,' The ratio of (H2~C0?/N2=3.1. After the stage of bhe secon- ' '''' dary conversion the dssired product was delivered bo bhe ., :;.' `.
stage of the primary s,beam,conversion, wherein ib was cooled .. ~`
to the temperature Df 620C giving its heab to the endDther- ,, .',.
mal conversion Df mstbane Dccurring at bhis sba~e.
Example 3 ~ '."',.
A mixtur~ of propane and butane in bhe ratio Df 2:1 res- ,'.'~.. '.
pectively under the pressure of 8.0 MPa was mixed wit~ steam in the ratio of H20/C _3:1 and was supplied, at the tiempe~
rature o~ 500C, tD the stags Df bhe primary sbeam conversiDn, wherefrom it was withdrawn at the ttemperature of 826C .'~
wlth the cDntenb Df meth9ne Df 17.8%.~he aDnvertad gas after '','~
the stage Df bhe primary steam:cDnversion was supplied tD the ,'.~.~.', sta~e of bhe secondary sbeAm-oxy~en conver~ion. Al90 fed to .... : -j'`; l ` ` : :
!"~
! I
2 ~ 7 4 ~
this stage was an Dx~/gen-hydrDcarb~n mixture h~ated tD the temperaturs of 5~0C and having the ratiD of C02/02=6:1. `:; ;.
How0v0r, insignificant fluctuations Df th~ paramet~rs of the :.
prDcscs str~ams result~d in vari.atiDns of tamp9raturs aft~r the s=cDndary cDnv~rsiDn frDm 970 tD 950C, while the con-tsnb o~ residual m~thane changed frDm 0.49 to 0. 70%. At va~
riations Df the desired product bemperature aftdr the sccon~
dary conversiDn from 970 to 950C the content D~ residual ~-msthans and tempsrature after ths primary steam aonversion ~ -changed: frDm 17.8 to 19.7% of CH4, while temperatur0 chang~d from 826 to 810C~ In thus cass, when an DxyOen~containing ~.
mixture after th= =t=8e of the secDndary stsam conversiDn ~ .
was supplied into the desirsd product in an amount Df from : ~;
0.1 to 9.0% by volume, the temp9rature prior tD the prlmary cDnv~rsion and, hencs, th3 cDmposition after tha:~
primary cDnv~rsiDn .~f~uld bs 9tabiliz0d. ``
An avsrag0 temp~r~tur= Df bh~ de=ir9d product priDr tD
the introductiDn thsrslnto of a~:smaller portlon o~ the oxyg~n-Gontainlng gas wa~= 960C and, 3ftsr th9 admission, 970C. ~h~ cDntsnt Df resid~u=l:m=thans in the d=sir0d ~ :
product was~0.5% by volume.~After th= stage Df th~ se`condary cDnv~rsion th~ desirsd prDduct was deiivered tD~th= stags Df :
th=~prlmary st=am co~nver=lon, wh~rcin it was.coDled to the tempsrabure of 570C:giving its h0at to tha ~ndDbhsrmal steam conv~rsion of methan0 occurri ng a t this stag=. ~ -;
.~ ~"'' ,., i,: , , , ~, -. "~-: . ,-:, .:. :. ., , ,: , , . ~ . :
, ~:,., ' - . . .- : ~ : . .
. , ,,~,," ~, ,;, ., , . . . . . . , ~ , .
r"S . ', :
~ -16-~: . '', -,'.
Exa mp l s 4 . . .
Natural gas D~ the fDllDwing compDsitiDn: CH4=92.8%, ~;
2 6 3 ~ 9Yo~ C3Hg-1. 1%~ C4H10=Oo 5%~ N2=1- ~a~ C02=0- 1% und~r the prassure of 4~3 ~a was mixed with steam in the ratiD
of stsam tD hydrocarbon -3:1, heatsd to the temperatur9 570C and fed tD the st`age D:~ an adiabatic preliminary ~-conversiDn, whersin at the account Df a physical heab Df the steam-gas mixture thare Dccurrad a prDcess Df a steam conversiDn with cDoling Df the reactiDn mixture tD the t~m~
perabure Df 490QC. The gas after the praliminary cDnversiDn had the fDllDWillg CDlllpDSitiDtl: C0=0~07~o~ C02=2-50%~ H2=9.32%~
CH = 22.21%, H20 = 65~o by vDlume, N2=0.90%. ~`
he ga9 aftsr the praliminary conversion was delivared ~ `
tD the stags Df the primary steam convarsion, wharefrom it `~ ~`
was withdrawn at the temp~laturs Df 754C and with the con-tent of CH4 in the dry converted gas equal to 21.20~o. The cDnverted gas after the 9tage Df the primary steam cDnversion was d~liverad to the stage Df the secDndary steam-oxygen cDnversiDn. Fed to the same stage was alSD a steam-air mix- ;~
tura heatad to the~temp~rature Df 500C and havlng the H20/02 ratio 0qual tD 0.5.~The de9ired prDduct t~mparature ~
at the outlet from tha secDndary 9team ~x,ygen cDnvsrsiDn ~ ~`
``~ `stage~ was 970C, tha cDntent of msthane ~,las 0.5~0~and th~
ratlo ~H2+C0)~/N2=2.08. After ths stage of tne secDndary conversion the desired product was delivered to the~stag~
of tha~primarg 9team cDrlversiDn, wherein it wa9 coDled bo the tempsrature Dfi 540C giving its heat bD the endothermal r steam conversiDn Df msthane.
~ . ,, ,.. .. . ~. :. : . : . :
2 !~ 2 ~ 7 4 ~
~ Example 5 .``~ The starting steam-hydrocarbQn mixture of ~xample 4 ~; was heated tD tha t3mp~raturs of 540C and deliv3red to tha ~stage Df an adiabatic prsliminary conversion, whsrain a~ ~-prDcess of stsam cQnvsrsion with cDoling zf the reacting mix~
tur~ tD the tsmp~raturs o~ 470C Dccurred due tD a physica~
; b~at Df the vapDur-gas mixtura. Ths temparatur~ of preh~3ting f ths stsam-air mixture witb the ratiD of H20/02=0.5 was~
600C. The temperature Df tb~desirad prDduct aftex coDling : `
3 at ths sta~e Df the primary conversi~n was 540C and ths ratio of (H2+C0)/N2=2.08. ;~ :
xample 6 `~
Nabural gas of tbe fDllDwiDg CDmpDsition CH4-92.8%, 2 6 3 9%~ C3H8~ %~ C4H1O=-5%~ N2=1 ~ 6~0~ CO _ OD 1YO under bhe pressurs Df 4.3 MPa was mixsd wit.~ sbsam in the ratio of steam to ths~hydrDcarbon of 4:1, hsated tD the tampsrature :.-~; : D~ 570C and supplied tD the stage:Df an adiabatic~preliminary :~ cDnversion, whare1n at the~accDun~b~Df a physical haat frDm ths steam-gas mixture a~process of steam converslDn tDok place with coDling of the rsact~ing mixture to th~ tempsratur3 of 485C. ~h~ ga:s after the preliminary cDnversiDn had the : fDllDwing composition: C0 = 0.05yo~ C02=2.35~o1 H2=8.86%, ~;:
CH =: 17 . 55~0~ N2=0.69~o~H20 =70,5%.~he gas after the prelimi~
nary cDnversiDn was deliver:ed~ bo tb~ stage Df th~ primary ;~ `
st:eam cOnverslon, wbarefrom it was withdrawn at the bempera~
t~ure Df 760C and with bh9 oDntent of CH4=15.38~0 in the dry converted gas. The cDnvertsd gas after the stag~ of the , :
2~2~7~
.
' ! -18-~,, . ~.
primary conv~rsiDn was deliver~d to the stage of the secon-dary steam-o~ygen conversion. A1SD fed tD this stage was ;~
- a stsam-Dx~g~n-nitrDgen mixture heated to the temperature ~-f 750C with tha ratio o~ (N2+H20)/02=5.47, the ratiD o~
H20/02 bein~ equal bo 0.59. In the case o~ availability ;1 o~ nitrDgen under pres~ure, it was used as an additive ~-~
to thc prDcess air. ~he desired producb tamperature at - ~`
tba outlet from the stage o~ th~ sacDndary sbeam-oxygen-nit-rogen conversiD~ was 940C, the content of methane - 0.~%, -1~ the ratio Df (H2+C0)/N2 = 2.08.
t~ A~ter thc stage of the secondary conversion the desir=d product was delivered to the stage of the primary steam con-v=rsion, wber=in It wa= cooled to the temperaturs of 540~C, ;~
;~ ~ giving it= beat tD bhe endotbermal sbeam conversiDn Df me-tbane.
' ',',' ,'. ,;
,~ ,.',,.'. ,,`
` ~ ; ' ,,j~",.,",
Claims (4)
1. A process for producing a hydrogen-containing gas comprising:
- mixing of a hydrocarbon feedstock with steam to give a steam-gas mixture;
- a preliminary steam catalytical conversion of said steam-gas mixture;
- a primary steam catalytical conversion of the preli-minarily converted said steam-gas mixture;
- mixing of an oxygen-containing gas with a heat-trans-fer agent in a volume ratio of the heat-transfer agent: oxygen equal to 0.5:30.0;
- heating of said oxygen-containing gas mixed with the heat-transfer agent to a temperature of a maximum value of 900°C;
- a secondary steam-oxygen catalytical conversion of the steam-gas mixture fed from said primary conversion;
- supplying, to said secondary conversion, of said oxy-gen-containing gas heated to said temperature and mixed with the heat-transfer agent;
- preparation of the desired product by effecting said secondary conversion;
- delivering said desired product to said primary conversion to carry out a process of a steam conversion by the heat from said desired product.
- mixing of a hydrocarbon feedstock with steam to give a steam-gas mixture;
- a preliminary steam catalytical conversion of said steam-gas mixture;
- a primary steam catalytical conversion of the preli-minarily converted said steam-gas mixture;
- mixing of an oxygen-containing gas with a heat-trans-fer agent in a volume ratio of the heat-transfer agent: oxygen equal to 0.5:30.0;
- heating of said oxygen-containing gas mixed with the heat-transfer agent to a temperature of a maximum value of 900°C;
- a secondary steam-oxygen catalytical conversion of the steam-gas mixture fed from said primary conversion;
- supplying, to said secondary conversion, of said oxy-gen-containing gas heated to said temperature and mixed with the heat-transfer agent;
- preparation of the desired product by effecting said secondary conversion;
- delivering said desired product to said primary conversion to carry out a process of a steam conversion by the heat from said desired product.
2. A process according to Claim 1, wherein as the heat-transfer agent steam and/or carbon dioxide is used.
3. A process according to Claim 1, wherein prior to said mixing with the heat-transfer agent the oxygen-containing gas in an amount of from 0.1 to 2.0% by volume of its total amount is withdrawn and mixed with the desired product prior to delivering thereof to the primary conversion.
4. A process according to Claim 1, wherein said preli-minary catalytical steam conversion is carried out at an initial temperature of 540-570°C.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SU894736269A RU1770265C (en) | 1989-09-20 | 1989-09-20 | Method of hydrogen-containing gas production |
SU4736269 | 1989-09-20 | ||
SU894745475A RU1770266C (en) | 1989-10-13 | 1989-10-13 | Method of hydrogen-containing gas production |
SU4745475 | 1989-10-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2025740A1 true CA2025740A1 (en) | 1991-03-21 |
Family
ID=26666215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002025740A Abandoned CA2025740A1 (en) | 1989-09-20 | 1990-09-19 | Process for producing hydrogen-containing gas |
Country Status (10)
Country | Link |
---|---|
CN (1) | CN1050363A (en) |
CA (1) | CA2025740A1 (en) |
DE (1) | DE3991744T (en) |
DK (1) | DK95391A (en) |
ES (1) | ES2022042A6 (en) |
FR (1) | FR2652073A1 (en) |
GB (1) | GB2244494A (en) |
IT (1) | IT1242707B (en) |
PT (1) | PT95234A (en) |
WO (1) | WO1991004222A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1069070B1 (en) * | 1999-07-15 | 2011-11-30 | Haldor Topsoe A/S | Process for the catalytic steam reforming of a hydrocarbon feedstock |
CN110055109B (en) * | 2018-04-08 | 2024-05-03 | 新能能源有限公司 | Gasifying agent conveying control method and system for fluidized bed gasifier |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2940840A (en) * | 1956-12-31 | 1960-06-14 | Hercules Powder Co Ltd | Hydrocarbon conversion process |
US3031286A (en) * | 1958-09-03 | 1962-04-24 | Basf Ag | Flameless reaction of sulfur-containing gaseous hydrocarbons to form carbon monoxide and hydrogen |
ES279922A1 (en) * | 1961-09-14 | 1963-01-16 | The M W Kellog Company | A procedure for the production of a rich gas mixture in hydrogen (Machine-translation by Google Translate, not legally binding) |
DE3480192D1 (en) * | 1983-03-25 | 1989-11-23 | Ici Plc | Steam reforming |
GB8308343D0 (en) * | 1983-03-25 | 1983-05-05 | Ici Plc | Steam reforming |
GB2163449B (en) * | 1984-07-18 | 1988-06-02 | Shell Int Research | Production of gas mixtures containing hydrogen and carbon monoxide |
GB8609099D0 (en) * | 1986-04-15 | 1986-05-21 | British Petroleum Co Plc | Production of synthesis gas |
EP0303438A3 (en) * | 1987-08-14 | 1989-12-27 | DAVY McKEE CORPORATION | Production of synthesis gas from hydrocarbonaceous feedstock |
-
1989
- 1989-12-08 DE DE19893991744 patent/DE3991744T/de not_active Withdrawn
- 1989-12-08 WO PCT/SU1989/000305 patent/WO1991004222A1/en active Application Filing
-
1990
- 1990-09-06 PT PT95234A patent/PT95234A/en not_active Application Discontinuation
- 1990-09-11 FR FR9011222A patent/FR2652073A1/en active Pending
- 1990-09-13 IT IT04827190A patent/IT1242707B/en active IP Right Grant
- 1990-09-13 ES ES9002370A patent/ES2022042A6/en not_active Expired - Fee Related
- 1990-09-19 CA CA002025740A patent/CA2025740A1/en not_active Abandoned
- 1990-09-20 CN CN90107959.6A patent/CN1050363A/en active Pending
-
1991
- 1991-05-20 GB GB9110895A patent/GB2244494A/en not_active Withdrawn
- 1991-05-21 DK DK095391A patent/DK95391A/en unknown
Also Published As
Publication number | Publication date |
---|---|
DK95391A (en) | 1991-07-02 |
IT1242707B (en) | 1994-05-17 |
DE3991744T (en) | 1991-10-10 |
FR2652073A1 (en) | 1991-03-22 |
WO1991004222A1 (en) | 1991-04-04 |
IT9048271A1 (en) | 1992-03-13 |
CN1050363A (en) | 1991-04-03 |
ES2022042A6 (en) | 1991-11-16 |
GB9110895D0 (en) | 1991-07-24 |
DK95391D0 (en) | 1991-05-21 |
GB2244494A (en) | 1991-12-04 |
PT95234A (en) | 1991-05-22 |
IT9048271A0 (en) | 1990-09-13 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
FZDE | Discontinued |