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US3287436A - Recovery of h2s and nh3 from olefin cracking - Google Patents

Recovery of h2s and nh3 from olefin cracking Download PDF

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Publication number
US3287436A
US3287436A US314047A US31404763A US3287436A US 3287436 A US3287436 A US 3287436A US 314047 A US314047 A US 314047A US 31404763 A US31404763 A US 31404763A US 3287436 A US3287436 A US 3287436A
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US
United States
Prior art keywords
diluent
vapor
sulfur
cracking
radicals
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
US314047A
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English (en)
Inventor
Brian J Ozero
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.)
Halcon Research and Development Corp
Original Assignee
Halcon International Inc
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 Halcon International Inc filed Critical Halcon International Inc
Priority to US314047A priority Critical patent/US3287436A/en
Priority to NL6410523.A priority patent/NL156120B/xx
Priority to GB37618/64A priority patent/GB1066869A/en
Priority to BE653135D priority patent/BE653135A/xx
Priority to LU47003A priority patent/LU47003A1/xx
Priority to CH1283764A priority patent/CH511775A/fr
Priority to FR990091A priority patent/FR1434147A/fr
Priority to SE11927/64A priority patent/SE303815B/xx
Priority to ES0304635A priority patent/ES304635A1/es
Priority to DE1468042A priority patent/DE1468042C3/de
Application granted granted Critical
Publication of US3287436A publication Critical patent/US3287436A/en
Assigned to HALCON RESEARCH AND DEVELOPMENT CORPORATION reassignment HALCON RESEARCH AND DEVELOPMENT CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HALCON INTERNATIONAL, INC.
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/14858—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with inorganic compounds not provided for before
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes

Definitions

  • This invention relates to processes for recovering H2S or the like catalytic material from the reaction mixture resulting from a reaction step carried out in the presence of SH radicals and an inert diluent and recycling the SH providing material together with diluent to the reaction step, and more particularly to an olefin cracking process wherein the reacted material is contacted with aqueous ammoniacal solution as a scrubbing agent to remove a mixture of H2S or the like material with ammonia which is also an inert diluent, and recycling this mixture to the reaction step in vapor form and it relates especially to such a process for cracking six carbon atom olefins which are isoprene precursors wherein the vapor mixture to be cracked is introduced to a cracking zone at an elevated pressure, eg., of about 100 p.s.i.a. and cracked. Additionally, the sulfur content of the recycled vapor is higher than the sulfur content of the aqueous solution from which it is
  • the olen cracking process comprises subjecting a cracking mixture comprising at least one olefin having in its molecule a carbon-to-carbon bond in a position beta to the double bond together with a source of SH radicals to elevated temperatures for periods of time suitable for cleaving the carbon-carbon bond which is in a position beta to the double bond. of said olen.
  • the conditions of cracking which .may be employed in this invention may be widely varied, depending upon the particular olefin to be cracked and the products desired.
  • the cracking temperature may be varied from about 300 C. to about 1000 C.
  • the time that the olens are in the cracking Zone during the p-ractice of this invention may range broadly from about 0.001 to about 3 seconds. However, it is preferable that times varying from 0.05 to 1.0 second and most preferable 0.1 to 0.5 be employed. These times are referred to usually as residence times and are usually defined as the time required for one mol of incoming gas, be it pure olefin or mixtures with other oleiins or diluents, to pass through the cracking zone.
  • the oleins are fed to the cracking reactor either as pure olens or in mixture with other olens or in mixture with some inert diluent. It is usually desirable to employ a diluent such as steam, carbon dioxide, hydrogen or parafns such as methane, ethane, propane, butanes, penetanes, and olefins such as ethylene and protanes, pentanes, and olens such as ethylene and propylene and butene-2 and the like. These hydrocarbons do not crack at the temperatures employed to crack the olens in the practice of this invention. Of these, steam is preferred because of economy. Propane and pentane may in some cases be preferred in the place of steam.
  • a diluent such as steam, carbon dioxide, hydrogen or parafns such as methane, ethane, propane, butanes, penetanes, and olefins such as ethylene and protanes
  • the ratio of diluent to olefin employed in the practice of this invention may be widely varied from about 0.5/ l
  • diluent to olen ratio ranging from about 2.0/1 to The olens may also be cracked without diluent.
  • the pressures employed in the cracking zone while cracking olens may be varied from about 10 millimeters of mercury ⁇ to 500 pounds per square inch gauge. How' ever it is preferred that the pressure range from about atmospheric to about pounds per square inch gauge with about 1 to about 2 atmospheres being most preferred.
  • the SH radical which is employed to increase the eiciency obtained when olefns are cracked in accordance with the practice of this invention may be provided by Various means. Hydrogen sulphide will under the conditions employed in the practice of this invention dissociate to form hydrogen and an SH radical. Low molecular weight mercaptans such as ethyl, normal propyl, isopropyl, normal butyl, isobutyl and the a-myl and hexyl mercaptans will also form an SH radical at the temperatures employed in the cracking operation. Sulphur could possible be employed. to produce SH radicals since under the conditions of the cracking there is some free hydrogen which would be available to combine with sulphur at the cracking temperature to give the SH radicals. Of these methods which may be employed normal propyl mercaptan and hydrogen sulphide are the preferred materials with which to supply SH radicals in the practice of this invention.
  • the SH radical employed in the practice of this invention may be used in amounts varying from about 0.5 to about 50 mol percent of SH radical based on the total mols ofthe olefin to be cracked. It has been found, however, that excellent results have been obtained by employing from about 5 to about 10 mol percent of the SH radical. It should be noted that one mol of the SH radica-l is produced for each mol of the SH radical producing compound employed.
  • a process for recovering a source of SH radicals fromthe reaction product of a reaction step carried out in the presence of SH radicals as catalyst and an inert diluent and recycling the sulfur-containing material and diluent to said reacti-on step comprises contacting said reaction product with aqueous ammoniacal solution whereby most of the sulfur-containing material is absorbed by said aqueous solution, separating and stripping the sulfur-rich aqueous solution with the diluent which functions las a volatile inert stripping agent to form a vapor mixture containing the source -of SH radicals toget-her with diluent and ammonia, and passing said vapor mixture to said reaction step;
  • reaction step is cracking an olen having in the molecule a carbon-to-carbon bond in a position beta to the double bond, the presence of from about 2 to about 10 mol percent of SH radicals;
  • the stripper 11 is fed liquid via line 13 (after heating in exchanger 16) which is contacted with high pressure steam fed via line 12 (or optionally via reboiler 12a).
  • the resulting bottoms fraction is removed via line 14 and usually at least some of it is sewered.
  • a part thereof is passed via line 15 (cooled in exchanger 16) to surge vessel 28.
  • the overhead from the stripper (steam, H28 and NH3) is passed via line 17 to reactor furnace 18 wherein it contacts the hydrocarbon feed fed via line 19.
  • the product resulting from the cracking is passed via line 20 to quench column 211 wherein it contacts recirculated, cooled liquid fed via line 22.
  • the resulting liquid is passed via lines 23 and 15 to quench surge vessel 28 wherein the condensed hydrocarbon phase forms an upper layer.
  • the gaseous overhead from column 21 is passed via line 24 to condenser 25 (quench solution being mixed therein, fed via -line 31) n and then Via line 26 to knock-out pot 27.
  • Aqueous liquid and condensed hydrocarbons are passed from pot 27 via line 34 to vessel 33.
  • the lower aqueous layer is passed from vessel 28 via line 29 to cooler 30' where it is cooled and then via line 22V to column 21.
  • the upper hydrocarbon layer is passed from vessel 28 via lines 32 and 34 to surge vessel 33 wherein two layers separate, the upper hydrocarbon layer being passed via line 46 to hydrocarbon purification.
  • the bottom aqueous layer from vessel 33 is passed via line 13 to stripper 11. From pot 27, vapor is passed via line 35, compressed in compressor 36,
  • the columns are of usual design, and may be of packed, tray or the like types. Additional coolers, scrubbers, and the like may 'be included if desired t-o scrub the liquid and/ or vapor hydrocarbon more completely.
  • Make-up NH3 and H28 are introduced via line 47 into vessel 28.
  • Example 1 Using the above described system, a mixture of 2- methyl pentene-Z and Z-methyl pentene-l is cracked at about 650 C., and the resulting reacted gas stream contains about 2.1 wt. percent H28, 3.36% NH3, 36.8% H2O and the remainder a mixture of hydrocarbons, mostly C5 and C3 hydrocarbons. About 8,000 lbs/hr. of this mixture is cooled to 130 F. by contacting with aqueous ammoniacal solution, a part thereof condensing to form a lower aqueous layer, and an upper hydrocarbon layer. The uncondensed part contains hydrocarbons and some H2S and NH3 and this is further condensed by chilling to 60 F.
  • the aqueous liquid is stripped with steam at a pressure ofvlOO p.s.i.a. to vgive a vapor at about 325 F. containing about 5 wt. percent H28, about 8% NH3 and about 87% H2O.
  • This vapor is fed at about 33,500 lbs/hr. into a cracking reactor along with hydrocarbon feed which is mainly isoprene precursors having six carbon atoms in the molecule, the hydrocarbon feed rate being about 46,000 lbs./hr.
  • the stripper liquid now essentially free of H2S and NH3, is recycled back to the absorption system.
  • the aqueous solution to the stripper contains 4 Wt. percent H28, the actual concentration depending on the quantity of stripped liquid leaving the column to be recycled. This quantity is chosen, as desired, preferably for most economical operation.
  • HZS is provided in a vapor form, at the desired concentration 'and pressure for the catalytic reaction step, and the use of intermediate compressors is completely avoided.
  • the steam used for stripping the H28 from the absorbing liquid remains in vapor form for use as diluentinstead of being condensed and separated (as it would be in the conventional system), thus providing steam economy.
  • the stripped aqueous liquid is recycledV to the absorption fand cooling system where it regains its former concentration of VH28 and NH3. This recycle minimizes or avoids troublesome waste disposal problems.
  • the vaporized hydrocarbon could be used as the H28 stripping medium, e.g. methane, ethane, propane, 4or the like, instead of steam. If little or no diluent steam were required, the use of the hydrocarbon for stripping would lower the heating cost.
  • the scrubbing liquid is Water containing ammonia and H28 (the ratio may vary from 1 to 5 parts by weight of NH3 per part of H28).
  • the H28 concentration in the circulating aqueous streams varies from about 0 up to about 5% by weight, as the lean liquor is enriched, and then stripped and recycled.
  • the temperature may be in the range of about 135 to about 180 C. at the corresponding pressure in the range Vof 50 to 150 p.s.i.'a.
  • the system is operable for use with any reactor pressure, and this sets the minimum stripping pressure, for feeding vapor directly to the reactor.
  • the stripper vapor usually contains about 2 to 10 mol percent of H28, the amount being selected to give the desired H28 concentration in the reactor.
  • the vapor contains H2O and NH3, the ratio of NH3 to H28 being about the same as or somewhat lower than mentioned above.
  • the concentration of NH3 is not critical since it is a diluent as is steam in the reactor.
  • a process for recovering a source of SH radicals from the reaction product of a reaction step carried out in the presence of SH radicals -as catalyst and an inert diluent, and recycling the sulfur-containing material and diluent to said reaction step which process comprises contacting said reaction product with aqueous ammoniacal solution whereby most of the sulfur-containing material is absorbed by said aqueous solution, separating and stripping the sulfur-rich aqueous solution with the diluent which functions as a volatile inert stripping agent to form a vapor mixture containing the source of 8H radicals together With diluent and ammonia, and passing said vapor mixture to said reaction step.
  • a process of claim 1 w-herein steam is the stripping agent and the stripping step is carried out at an elevated pressure suiciently high to give a recycled vapor mixture at the ⁇ desired inlet pressure for the elevated pressure reaction Step.
  • reaction step is cracking an olefin having in the molecule a carbon-to-carbon bond in a position beta to the ⁇ double bond, in the presence ⁇ of from about 2 to about 10 mol percent of SH radicals.
  • a process of claim 8 wherein the recycled vapor mixture is .at about p.s.i.a., the sulfur-rich aqueous iammoniacal solutions are mixed together and the resulting solution contains not over about 5 wt. lof sulfur-containing material calculated as H28, the vapor containing at least 2 mols percent of sulfur-containing material calculated as H28.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US314047A 1963-10-04 1963-10-04 Recovery of h2s and nh3 from olefin cracking Expired - Lifetime US3287436A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US314047A US3287436A (en) 1963-10-04 1963-10-04 Recovery of h2s and nh3 from olefin cracking
NL6410523.A NL156120B (nl) 1963-10-04 1964-09-10 Werkwijze voor het kraken van alkenen, in aanwezigheid van een bron van sh-radicalen en waterdamp.
GB37618/64A GB1066869A (en) 1963-10-04 1964-09-15 Recovery of sh radicals
BE653135D BE653135A (xx) 1963-10-04 1964-09-16
LU47003A LU47003A1 (xx) 1963-10-04 1964-09-23
FR990091A FR1434147A (fr) 1963-10-04 1964-10-02 Procédé chimique de récupération d'acide sulfhydrique
CH1283764A CH511775A (fr) 1963-10-04 1964-10-02 Procédé de récupération d'une source de radicaux SH d'un milieu réactionnel
SE11927/64A SE303815B (xx) 1963-10-04 1964-10-03
ES0304635A ES304635A1 (es) 1963-10-04 1964-10-03 Procedimiento de recuperacion de una fuente de radicales sh.
DE1468042A DE1468042C3 (de) 1963-10-04 1964-10-05 Verfahren zum Spalten von Olefinen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US314047A US3287436A (en) 1963-10-04 1963-10-04 Recovery of h2s and nh3 from olefin cracking

Publications (1)

Publication Number Publication Date
US3287436A true US3287436A (en) 1966-11-22

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US314047A Expired - Lifetime US3287436A (en) 1963-10-04 1963-10-04 Recovery of h2s and nh3 from olefin cracking

Country Status (9)

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US (1) US3287436A (xx)
BE (1) BE653135A (xx)
CH (1) CH511775A (xx)
DE (1) DE1468042C3 (xx)
ES (1) ES304635A1 (xx)
GB (1) GB1066869A (xx)
LU (1) LU47003A1 (xx)
NL (1) NL156120B (xx)
SE (1) SE303815B (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622646A (en) * 1969-06-11 1971-11-23 Cities Service Co Process for cracking cycloolefins

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107416775A (zh) * 2017-09-19 2017-12-01 江苏科瑞工程设计有限公司 一种含氨酸性气和废硫酸的低氮裂解工艺

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3238270A (en) * 1961-12-15 1966-03-01 Sinclair Research Inc Production of isoprene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3238270A (en) * 1961-12-15 1966-03-01 Sinclair Research Inc Production of isoprene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3622646A (en) * 1969-06-11 1971-11-23 Cities Service Co Process for cracking cycloolefins

Also Published As

Publication number Publication date
SE303815B (xx) 1968-09-09
BE653135A (xx) 1965-03-16
DE1468042C3 (de) 1978-04-06
DE1468042B2 (de) 1977-08-04
GB1066869A (en) 1967-04-26
ES304635A1 (es) 1965-04-01
CH511775A (fr) 1971-08-31
NL6410523A (xx) 1965-04-05
LU47003A1 (xx) 1966-03-23
NL156120B (nl) 1978-03-15
DE1468042A1 (de) 1969-07-24

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