US3876753A - Process for producing carbon bisulfide - Google Patents

Process for producing carbon bisulfide Download PDF

Info

Publication number
US3876753A
US3876753A US355992A US35599273A US3876753A US 3876753 A US3876753 A US 3876753A US 355992 A US355992 A US 355992A US 35599273 A US35599273 A US 35599273A US 3876753 A US3876753 A US 3876753A
Authority
US
United States
Prior art keywords
stream
sulfur
hydrocarbon
outlet
section
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.)
Expired - Lifetime
Application number
US355992A
Other languages
English (en)
Inventor
James L Manganaro
Morton Meadow
Sidney Berkowitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
FMC Corp
Original Assignee
FMC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by FMC Corp filed Critical FMC Corp
Priority to US355992A priority Critical patent/US3876753A/en
Priority to CA196,614A priority patent/CA1011533A/en
Priority to AR253345A priority patent/AR198748A1/es
Priority to NL7405253A priority patent/NL7405253A/xx
Priority to GB1818874A priority patent/GB1467321A/en
Priority to AT348574A priority patent/AT338836B/de
Priority to JP49047165A priority patent/JPS5013295A/ja
Priority to BR3471/74A priority patent/BR7403471D0/pt
Priority to IT22084/74A priority patent/IT1010246B/it
Priority to FR7414812A priority patent/FR2227223B1/fr
Priority to SE7405773A priority patent/SE403764B/xx
Priority to ES425835A priority patent/ES425835A1/es
Priority to BE143811A priority patent/BE814423A/fr
Priority to DE2420939A priority patent/DE2420939C2/de
Application granted granted Critical
Publication of US3876753A publication Critical patent/US3876753A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/70—Compounds containing carbon and sulfur, e.g. thiophosgene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00159—Controlling the temperature controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure

Definitions

  • a stream of hydrocarbon gas is fed co-current with a hot stream of sulfur vapor and the cross section of the sulfur vapor stream is decreased locally at the zone where it is brought into contact with the hydrocarbon stream so as to form a converging sulfur stream.
  • the sulfur vapor may be caused to travel the path of a converging cone whose apex lies along the centerline of the hydrocarbon stream.
  • FIGS. 1, 2 and 3 are crosssections of various embodiments.
  • FIG. I shows an arrangement particularly suitable for use in a relatively small scale installation, in which the stream velocities (and Reynolds numbers) are not high.
  • FIGS. 2 and 3 show arrangements suitable for a large scale installation with high stream velocities.
  • the arrangement shown in FIG. 2 (like that of FIG. 1) has a pressure recovery section, while that of FIG. 3 has no pressure recovery section.
  • FIG. I the flow of the streams is from right to left.
  • the heated sulfur vapor is introduced through a pipe 11 of circular cross section in an annular stream around a coaxial hydrocarbon feed tube I2.
  • the latter is also of circular cross section; its inside diameter is 0.622 cm, its outside diameter is 0.953 cm, and its outlet end 13 is chamfered as shown.
  • a venturi insert 16 which fits securely within the otherwise uniform pipe II and which has an inwardly converging portion 17, a throat 18, and an outwardly converging (or pressure recovery) section 19.
  • the sulfur vapor stream is forced through a narrow gap 21 thus greatly increasing in velocity (Bernoullis principle) as it approaches and impinges upon the hydro carbon stream.
  • This increase in velocity increases the force ratio" of the outer (sulfur) stream to the inner (hydrocarbon) stream and increases the interpenetration and mixing of the two streams.
  • the force ratio is defined as M V /MN, where M and M, are the mass rates of flow of the outer and inner streams respectively and V and V, are the respective linear velocities of said streams. In the design shown in FIG. 1 this force ratio is in the neighborhood of 10, under the conditions specified in Example 1 below.
  • a gradually diverging section Downstream of the throat there is a gradually diverging section which, as is well known in nozzle design, serves as a pressure recovery section in which the velocity of the resulting mixed stream is reduced gradually and its pressure, which is lowest at the throat, increases correspondingly.
  • FIG. 2 Corresponding parts of FIG. 2 are numbered identically to those of FIG. 1.
  • the sulfurzhydrocarbon force ratio is about 2:l for the following operating conditions: hydrocarbon (natural gas) feed temperature 100C; sulfur feed temperature 680C; feed pressures about 6.5 atmospheres psig); excess sulfur (over that needed stoichiometrically for the reaction to form CS I5% mass rate of flow of sulfur 6,580 kg per hour.
  • FIG. 3 the parts are also numbered in the same way as FIG. I.
  • the insert 16 is a tapered reducer circumferentially welded (as indicated at 22) to the inner walls of the pipe I].
  • the insert I6 is chamfered at 45 as shown.
  • the mixture may be led through further lengths of hot tubes around bends and into contact with various surfaces such as packings; during this further travel, substantially all the methane in the feed may be reacted with the sulfur under noncatalytic or catalytic conditions.
  • hydrocarbon stream may contain substantial, even major, proportions of diluents, such as H 8 and/or CS
  • diluents such as H 8 and/or CS
  • sulfur stream too, may contain such diluents.
  • the volumes given represent, in accordance with standard practice, the volume calculated to standard conditions (STP) of a temperature of 0C and an absolute pressure of 760 mm Hg. Residence times are given in seconds and are equal to 3600 divided by space velocity" (S.V.) expressed in hours; S. ⁇ /. is the quotient of the total volume (in liters) of reactants at STP (with sulfur calculated as per hour, divided by the reactor volume (in liters).
  • Sulfur vapor preheated to 700C and natural gas preheated to 400C are brought together using the arrangement illustrated in FIG. I, located in an electric furnace. Downstream of the venturi the mixture passes through the pipe 11 which takes the form of four two foot long side by side parallel sections (of the same three-fou rths inch IPS, Schedule 40 stainless steel pipe) each of which is joined to its neighbor by a return elbow of the same stainless steel welded thereto so that the reaction mixture flows successively through the four sections in a sinuous path, all within the electric furnace.
  • the insert 16 is also made of stainless steel.
  • the reaction mixture After flowing through this tube (residence time 1 l seconds) the reaction mixture is then immediately quenched, first in a vessel at 140C (thereby condensing the sulfur in the reaction mixture).
  • the noncondensed gases including carbon bisulfide, then pass through a pressure-regulator, set to provide a back pressure of about 6.5 atmospheres (80 psig), from which the gases are passed to a condenser at C and 74 psig to condense carbon bisulfide; non-condensed gases are vented at atmospheric pressure.
  • the hydrocarbon is a natural gas of the following molar composition: 89.7 percent methane, 4.18 percent ethane, 1.7 percent propane, 2.2 percent butanes, 2.04 percent nitrogen and 0.1 percent water.
  • the sulfur is fed at a rate to provide an excess of percent with respect to stoichiometry; specifically, the rates of supply of sulfur and hydrocarbon are 578 g per hour and 88.3 liters (at STP) per hour respectively.
  • the temperature measured at the internal wall of the reactor pipe at point cm downstream of the venturi throat inlet is about 700C.
  • the conversion rate of the natural gas is quantitative and the carbon bisulfide has a purity of 9999+ percent with less than 12 ppm benzene and thiophene as trace impurities. There is no evidence of tar formation in the recovered sulfur.
  • EXAMPLE 2 In this Example the apparatus is similar to that de scribed in Example l but the arrangement of FIG. 3 is employed in a reactor pipe of 14.29 cm internal diame ter.
  • the hydrocarbon feed is natural gas having the following analysis (by mol percent): methane 96.35, eth ane 2.32, propane 0.25, isobutane 0.02, butane 0.02, isopentane 0.0], n-pentane 0.01, hexane less than 0.01 other hydrocarbons 0.02, nitrogen 0.44, C0 0.55, H 0.02.
  • the inlet pressure is about 6.3 atmospheres (about 78 psig), the sulfur is preheated to 664C, the hydrocarbon feed is preheated to 115C, the excess sulfur with respect to stoichiometry is 13 percent; the sulfur feed rate is 6,235 kg per hour and the hydrocarbon feed rate is 680 kg per hour. From the throat the mixture travels through a straight length of the pipe for about 9.] meters, then around a bend and through more of the same type of pipe in the furnace, then (its temperature being about 630-650C) enters a packed reactor chamber containing silica gel particles, after which sulfur and carbon bisulfide are successively condensed from the mixture in conventional manner. Carbon bisulfide is produced in very high yield and at very high purity, having especially low benzene content.
  • Example 2 In large scale operation, as in Example 2, the feed rates are such that the Reynolds numbers of the hydrocarbon stream and the sulfur stream (before it enters the reducing section) are often in the range of about 10 to 10.
  • the force ratio as previously defined, is above 2:1, specifically about 2.3:], and can readily be calculated from the data given in that Example.
  • the linear speed of the stream of hydrocarbon is often very much greater than the linear speed of the sulfur, before the sulfur stream starts to converge, e.g., well over 5 (such as about 10, 15, 20, 25 or more) times the linear speed of the sulfur.
  • the sulfur has speeded up but is nevertheless often still moving at a lower linear speed that the hydrocarbon stream, but because of the greater mass rate of flow of the sulfur the force ratio is. preferably, well above 0.5:1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Carbon And Carbon Compounds (AREA)
US355992A 1973-04-30 1973-04-30 Process for producing carbon bisulfide Expired - Lifetime US3876753A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US355992A US3876753A (en) 1973-04-30 1973-04-30 Process for producing carbon bisulfide
CA196,614A CA1011533A (en) 1973-04-30 1974-04-02 Production of carbon disulphide from sulphur vapors and a gaseous hydrocarbon
AR253345A AR198748A1 (es) 1973-04-30 1974-04-18 Procedimiento contino para producir bisulfuro de carbono por reaccion de azufre con hidrocarburo
NL7405253A NL7405253A (fr) 1973-04-30 1974-04-18
GB1818874A GB1467321A (en) 1973-04-30 1974-04-25 Manufacture of carbon disulphide
AT348574A AT338836B (de) 1973-04-30 1974-04-26 Verfahren und vorrichtung zum herstellen von schwefelkohlenstoff
JP49047165A JPS5013295A (fr) 1973-04-30 1974-04-27
BR3471/74A BR7403471D0 (pt) 1973-04-30 1974-04-29 Processo continuo para a producao de bissulfeto de carbono e aparelho empregado no processo
IT22084/74A IT1010246B (it) 1973-04-30 1974-04-29 Reazione fra zolfo e idrocarburi
FR7414812A FR2227223B1 (fr) 1973-04-30 1974-04-29
SE7405773A SE403764B (sv) 1973-04-30 1974-04-29 Kontinuerligt forfarande for framstellning av koldisulfid samt anordning herfor
ES425835A ES425835A1 (es) 1973-04-30 1974-04-30 Procedimiento continuo y aparato para la produccion de bi- sulfuro de carbono.
BE143811A BE814423A (fr) 1973-04-30 1974-04-30 Reaction entre le soufre et un hydrocarbure
DE2420939A DE2420939C2 (de) 1973-04-30 1974-04-30 Kontinuierliches Verfahren zur Herstellung von Schwefelkohlenstoff und hierfür verwendbare Vorrichtung

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US355992A US3876753A (en) 1973-04-30 1973-04-30 Process for producing carbon bisulfide

Publications (1)

Publication Number Publication Date
US3876753A true US3876753A (en) 1975-04-08

Family

ID=23399622

Family Applications (1)

Application Number Title Priority Date Filing Date
US355992A Expired - Lifetime US3876753A (en) 1973-04-30 1973-04-30 Process for producing carbon bisulfide

Country Status (14)

Country Link
US (1) US3876753A (fr)
JP (1) JPS5013295A (fr)
AR (1) AR198748A1 (fr)
AT (1) AT338836B (fr)
BE (1) BE814423A (fr)
BR (1) BR7403471D0 (fr)
CA (1) CA1011533A (fr)
DE (1) DE2420939C2 (fr)
ES (1) ES425835A1 (fr)
FR (1) FR2227223B1 (fr)
GB (1) GB1467321A (fr)
IT (1) IT1010246B (fr)
NL (1) NL7405253A (fr)
SE (1) SE403764B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090025935A1 (en) * 2005-04-14 2009-01-29 Johan Jacobus Van Dorp System and methods for producing oil and/or gas
US20090056941A1 (en) * 2006-05-22 2009-03-05 Raul Valdez Methods for producing oil and/or gas
US20150124554A1 (en) * 2013-11-07 2015-05-07 U.S. Department Of Energy Apparatus and method for generating swirling flow
US10711176B2 (en) * 2018-10-03 2020-07-14 David O. Trahan Method, process, apparatus and chemicals to produce and inject paraffin treating compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61205681A (ja) * 1985-03-09 1986-09-11 株式会社アスク 珪酸質塗膜の形成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3512219A (en) * 1965-10-19 1970-05-19 American Potash & Chem Corp Injection reactor for titanium dioxide production
US3699215A (en) * 1968-03-26 1972-10-17 Progil Production of carbon disulphide from hydrocarbons

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4893U (fr) * 1971-05-20 1973-01-05

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3512219A (en) * 1965-10-19 1970-05-19 American Potash & Chem Corp Injection reactor for titanium dioxide production
US3699215A (en) * 1968-03-26 1972-10-17 Progil Production of carbon disulphide from hydrocarbons

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090025935A1 (en) * 2005-04-14 2009-01-29 Johan Jacobus Van Dorp System and methods for producing oil and/or gas
US7601320B2 (en) * 2005-04-21 2009-10-13 Shell Oil Company System and methods for producing oil and/or gas
US20090056941A1 (en) * 2006-05-22 2009-03-05 Raul Valdez Methods for producing oil and/or gas
US8511384B2 (en) 2006-05-22 2013-08-20 Shell Oil Company Methods for producing oil and/or gas
US20150124554A1 (en) * 2013-11-07 2015-05-07 U.S. Department Of Energy Apparatus and method for generating swirling flow
US9956532B2 (en) * 2013-11-07 2018-05-01 U.S. Department Of Energy Apparatus and method for generating swirling flow
US10711176B2 (en) * 2018-10-03 2020-07-14 David O. Trahan Method, process, apparatus and chemicals to produce and inject paraffin treating compounds

Also Published As

Publication number Publication date
GB1467321A (en) 1977-03-16
NL7405253A (fr) 1974-11-01
IT1010246B (it) 1977-01-10
BE814423A (fr) 1974-10-30
JPS5013295A (fr) 1975-02-12
SE403764B (sv) 1978-09-04
DE2420939A1 (de) 1974-11-14
BR7403471D0 (pt) 1974-11-19
CA1011533A (en) 1977-06-07
FR2227223A1 (fr) 1974-11-22
DE2420939C2 (de) 1983-06-23
ES425835A1 (es) 1976-06-16
AR198748A1 (es) 1974-07-15
FR2227223B1 (fr) 1978-01-27
ATA348574A (de) 1977-01-15
AT338836B (de) 1977-09-12

Similar Documents

Publication Publication Date Title
US3927185A (en) Process for producing carbon disulfide
IE802254L (en) Production of olefins from hydrocarbons
US8747497B2 (en) Catalytic secondary reforming process and reactor for said process
US2257293A (en) Manufacture of hydrocarbons
US3876753A (en) Process for producing carbon bisulfide
US2486879A (en) Manufacture of hydrocarbons and the like
US2919976A (en) Conversion of hydrogen sulfide into free sulfur
US4051193A (en) Process for producing ethylene from ethane
CA2506223A1 (fr) Production de chloramine gazeuse
US3592602A (en) High turn-down ratio design for sulfur plants
US1449423A (en) Production of naphthyl amines
US5478962A (en) Process for the synthesis of dimethylcarbonate
US2882130A (en) Process for producing hydrogen sulfide and carbon bisulfide
Choudhary et al. Oxidative pyrolysis of methane to higher hydrocarbons: Effects of water in feed
US3699215A (en) Production of carbon disulphide from hydrocarbons
Gordon et al. The production of hydrogen from methane using tubular plasma reactors
US3063803A (en) Turbulent flow flame synthesis of hydrogen cyanide
CA1039027A (fr) Production de bisulfure par reaction de vapeur de soufre sur des gaz hydrocarbures
US3436181A (en) Process for manufacturing carbon disulphide
CN112142003B (zh) 一种一氧化碳变换工艺
US2578490A (en) Gas purification
US3667907A (en) Manufacture of hydrogen cyanide
US3278627A (en) Production of ethylene
Nelson et al. Isotopic labelling studies of the mechanism of the catalytic oxidative coupling of methane
US2610200A (en) Synthesis of hydrocarbons