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US3315004A - Process for cracking propylene and isobutylene in the presence of hbr - Google Patents

Process for cracking propylene and isobutylene in the presence of hbr Download PDF

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Publication number
US3315004A
US3315004A US263189A US26318963A US3315004A US 3315004 A US3315004 A US 3315004A US 263189 A US263189 A US 263189A US 26318963 A US26318963 A US 26318963A US 3315004 A US3315004 A US 3315004A
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United States
Prior art keywords
isobutylene
propylene
cracking
hydrogen bromide
hbr
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Expired - Lifetime
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US263189A
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English (en)
Inventor
Happel John
Charles J Marsel
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NL Industries Inc
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Nat Lead Co
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Priority to GB1051772D priority Critical patent/GB1051772A/en
Application filed by Nat Lead Co filed Critical Nat Lead Co
Priority to US263189A priority patent/US3315004A/en
Priority to DE19641468409 priority patent/DE1468409A1/de
Priority to LU45479A priority patent/LU45479A1/xx
Priority to BE644185D priority patent/BE644185A/xx
Priority to AT155264A priority patent/AT250317B/de
Priority to NL6401710A priority patent/NL6401710A/xx
Application granted granted Critical
Publication of US3315004A publication Critical patent/US3315004A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • 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
    • 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
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • C07C4/10—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from acyclic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/35—Formation of carbon-to-carbon triple bonds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/08—Halides

Definitions

  • This invention relates to a novel and improved catalytic thermal process for making mixtures of methyl acetylene and allene from isobutylene and/ or propylene.
  • the invention pertains to a process whereby isobutylene and/ or propylene is cracked under special conditions in the presence of a hydrogen .bromide or hydrogen bromide itself to give improved yields of the desired methyl acetylene and allene.
  • Prolonged contact time of the isobutylene feed in the cracking zone was found to cause breaking of the carbon chain of the isobutylene molecule to give predominantly carbon monoxide and acetylene.
  • Prolonged contact time has also been found to result in decreased yields of methyl acetylene and allene since these products are cleaved by thermal decomposition.
  • the contact time be sufliciently long to allow for the demethanization of the isobutylene molecule for production of the desired methyl acetylene and allene.
  • One Way to obtain this required close control on contact time is to cool rapidly the hot reactor exit gases to a point below which further significant thermal. decomposition will occur.
  • shock quenching This rapid cooling operation has been termed shock quenching. It has also been disclosed that steam is a particularly advantageous diluent to use when cracking at an overall pressure of one atmosphere or greater. This is true not only because of the fact that steam is an economical diluent and can readily be condensed out of the exit reactor gases, but also because steam suppresses the formation of coke and therefore decreases the loss of methyl acetylene and allene to this worthless product.
  • the basis of the present invention is the discovery that when isobutylene or propylene is cracked in the presence of hydrogen bromide or a hydrogen bromide yielding compound, the presence of the hydrogen bromide acts to direct and improve the cracking in such a way so as to increase the yield of the more valuable methyl acetylene and allene at the expense of the less desirable by-products of the cracking process.
  • an inert diluent preferably steam
  • FIGURE 1 shows the outstanding improvement in yield obtained by the catalyst addition. From actual operating data obtained, a smooth curve has been drawn through the points in the accompanying plot for the range of conversion. At high conversion levels, the presence of hydrogen bromide in the cracking process more than doubles the yield of desired products.
  • conversion in this specification is used to nean the ratio of the moles of propylene cracked to other )roducts per mole of propylene charged to the reactor for a single pass.
  • selectivity is used to mean 'atio of the moles of C H hydrocarbons (methyl acetyene and allene) obtained per mole of propylene con- ;umed to other products for a single pass.
  • yield as used in the specification means the ratio of the moles of C H hydrocarbons formed per mole of propylene feed to the reactor. Used this way, yield is also equal to the product of the conversion multiplied by the selectivity.
  • the accompanying graph of actual experimental data is a plot of yield versus conversion.
  • Table I A table (Table I) of actual experimental data is included hereinafter in the examples, to describe more fully the improvement obtained by hydrogen bromide yielding compound addition in the cracking of propylene. It will be noted from this table that the selectivity of the desired C H hydrocarbons obtained tends to increase with an increasing ratio of hydrogen bromide to propylene in the feed to the reactor. It will also be noticed that the increased yields of methyl acetylene and allene are achieved at the expense of the less useful byproducts of the cracking, which is most desirable.
  • FIGURE 2 of the actual experimental data is a plot of yield versus conversion. It will be noted from the accompanying graph (curve 2) that the yield drops off rapidly for higher conversions when cracking without catalyst addition. For cracking with hydrogen bromide (curve 1) addition, however, it will be noticed that yields steadily increase with conversion and reach a maximum at the very high conversion of about 80-85%, which is a highly desirable result for commercial operation. This a very unexpected and unpredictable result using hydrogen bromide or hydrogen bromide producing compounds, i.e., HBr forming at the conditions and with the materials in the cracking zone.
  • reaction zone contact time should be within the range of 0.0005 to 0.06 second, while the mole percentage of steam to olefin feed may be varied between 40 and 95 percent.
  • the preferred contact times are in the range of 0.001 to 0.005 seconds.
  • Reaction pressures for the isobutylene will vary from about 0.05 to 0.30 atmospheres or about 38 to 225 mm. Hg by dilution and total pressure may be kept conveniently at one atmosphere.
  • the molar ratio of hydrogen bromide to isobutylene may be varied from as low as required depending on the aims of the process up to a maximum which is dictated by economics.
  • the lower practical limit of hydrogen bromide to isobutylene was found to be about 5 moles of HBr per 100 moles of olefin feed, a point at which significant improvements in yield 5 over that obtained without HBr addition becomes apparent.
  • the optimum ratio of H131 to feed is governed generally by the economics of the particular process and will be determined by a balance between the cost of hydrogen bromide recovery and recycle and the savings in plant and operating cost obtained by the increased yields of methl acetylene and allene due to hydrogen bromide addition.
  • the preferred method of operation for propylene is from a mole ratio of superheated steam to propylene and propylene to hydrogen bromide of to 1 and 1 to 1 moles respectively, up to a mole ratio of superheated steam to propylene and propylene to hydrogen bromide of 4 to l and to 1 moles respectively.
  • the preferred contact time is from 0.0005 second to 0.01 second.
  • the effective temperature in the cracking zone is above 900 C. and ranges from 800 C. to 1250 C.
  • the maximum yield of methyl acetylene and allene is obtained at conversions of 70 to 90 percent of the feed.
  • the preferred method of operation for isobutylene is from a mole ratio of superheated steam to isobutylene and isobutylene to hydrogen bromide of 10 to 1 and 1 to 1 moles respectively up to a mole ratio of superheated steam to isobutylene and isobutylene to hydrogen bromide of 4 to 1 and 15 to 1 moles respectively.
  • the effective temperature range in the cracking zone is from 700 C. to 1150 C. At a temperature of about 800 C., the conversion is low (below 10%). At temperatures of about 1000 C., the conversion is high (above 90%) but the selectivity falls off. It appears that using the above defined reaction conditions, the maximum yield of methyl acetylene and allene is obtained at conversions of 80 to 90 percent.
  • a hot gaseous stream of superheated steam is added to the olefin feed stream, or
  • a portion of the olefin gas stream is burned and provides hot combustion gases, which heat up the main feed stream to the desired temperature range, or
  • Powdered particles of an inert material e.g., alumina are heated at elevated temperatures and injected into the olefin feed stream.
  • a particularly advantageous method of achieving the high temperatures for cracking with good control is to mix the olefin feed with superheated steam just prior to its entry into the cracking section.
  • the rapid mixing and dififusion of the two gases because of high velocity and high temperature will very rapidly bring the feed to the desired cracking temperature.
  • the superheated steam entering or admixed be at a temperature greater than that in the cracking zone since it will essentially determine the final temperature of the olefin, steam, and hydrogen bromide or hydrogen bromide yielding compounds, admixture entering the re actor.
  • Anotheradvantage of steam dilution is the fact that the cracking of isobutylene or propylene to methyl acetylene and allene is an endothermic reaction and thus heat is absorbed during the cracking resulting in a temperature drop within the reaction zone.
  • the high temperature steam dilution acts as a heat source to keep the cracking zone at a more constant temperature and provide more accurate control of contact time.
  • the high temperature steam necessary for this purpose can vary in temperature from 1000 C.
  • this temperature may be obtained in a variety of Ways, among them being the use of a high temperature pebble heater, the mixing of low temperature steam with the very hot steam product from the burning of hydrogen and oxygen to give the desired high temperature steam or the use of electrical heating.
  • the superheated steam diluent need not be sure, but may also be mixed with gases obtained by the combustion of a fuel. desirable, however, that the steam 1 since this will allow for substantially tion of the diluent from the cracked gases. This will reduce the problem of purifying these cracked gases since they enter the purification system undiluted by the extraneous gases of the dilution steam mixture.
  • Contact time is defined as the volume of the reaction zone divided by the volume of feed at the reaction temperature.
  • the cracking is an endothermic reaction and there is a varying temperature profile throughout the length of the reactor. Therefore, the proper integrated effective temperature must be used in order to determine the volume of the gaseous feed through the reaction zone.
  • the contact time may be varied by varying the rate of gases going through the reactor. Variation of temperature will also vary contact time by changing the volume of the feed through the reaction zone. Contact time can also vary for a given fixed feed by replacement with reactors of various volumes or using a series of reactors with fixed cross section but with varying lengths.
  • Rapid termination of contact time is best obtained by direct contact with a deluge of water or oil. It is also possible to contact the reaction zone gases with cool gases or powdered, inert material such as alumina, the method of cooling being unimportant so long as the exit reactor gases are cooled very quickly to below at least 500 C. This rapid cooling serves to prevent thermal decomposition of reaction products, prevent polymerization and to control contact time.
  • the hydrogen bromide additive of this invention may be added in many forms, as a liquid or vapor depending on the compound and the pressure. It is also possible to use an organic or mineral compound containing bromine which under the cracking conditions in the reactor decomposes to yield required amounts of a bromide of the form such that it is recovered as hydrogen bromide. mineral compound is used which liberates hydrogen bromide under the conditions in the reactor, it is convenient to dissolve it in water which is subsequently converted to steam and then acts as the inert diluent for cracking.
  • organic bromine compounds which may be used in the reaction are ethyl bromide, 2 bromopropane, l-bromobutane, and the like.
  • Mineral bromine compounds which may be used in the process of the invention are hydrobromic acid and water soluble bromine compounds. Suitable compounds in the scope of the invention must decompose or dissociate under the conditions of the reaction to form hydrogen bromide.
  • An economic method of introducing a hydrogen bromide yielding compound is to use HBr as the reagent. The mixture of HBr and steam after passing through the cracking zone is readily recovered in the quench system. If the exit gases from the cracking reactor are quenched with water, a dilute solution of the HBr originally fed is obtained. If the exit gases are quenched with another material such as an oil, the HBr dissolves in the condensed steam. Recovery of the HBr for reuse in the cracking zone may be accomplished by distillation, absorption or any other well known means.
  • This invention may be carried out with pure isobutylene or pure propylene or with a commercial fraction containing these compounds such as is obtained by distillation or extraction in a petroleum operation or the like.
  • Example 1 A propylene feed stream is metered and intimately mixed with superheated steam and HBr just before introduction into a 9" long schedule stainless steel reactor.
  • the mole ratio of steam to propylene is kept at about 6.7 to 1.
  • the temperature in the center of the reactor is about 1015 C, and the contact time is 0.00207 second.
  • the resulting propylene conversion is 55.6% and selectivity of allene and methyl acetylene obtained is 23.6% as determined by exit gas analysis. While these flows are held constant, HBr is added at a molar ratio of 0.078 mole of HBr per mole of propylene.
  • the temperature is determined to be 1028 C.
  • the resulting conversion is 56.3% and the selectivity of methyl acetylene and allene is 34.3% as determined by exit gas analysis.
  • the HBr mole ratio is then increased to 0.117 mole of HBr per mole of propylene.
  • the temperature is 1030 C. as read by a thermocouple. Conversion is 56.9% and selectivity is 39.1% as determined by exit gas analysis.
  • the HBr is then increased to 0.526 mole of HBr per mole of propylene, and temperature is determined to be 1020 C.
  • the conversion is 52.9% and selectivity is 50.4% as determined by exit gas analysis.
  • Example 2 A propylene feed stream is metered before being introduced into an experimental inconel cracking tube which is one-half inch schedule 80 and 11 inches long. Measured quantities of superheated steam and hydrogen bromide are then intimately mixed with propylene just prior to the reactor tube entrance. The superheated steam which has been previously heated in a zone where hydrogen-oxygen combustion is taking place, is passed into the reactor. The mole ratio of steam to propylene is 6.7 to 1. The total reactor pressure is kept at about one atmosphere during the reaction and a thermocouple in the middle of the cracking tube registers a temperature of 1080 C. The contact time of reaction as determined by the effective temperature is about 0.0036 second and the resulting conversion is 56.8%.
  • a water quench is used immediately following the reaction zone and after steam condensation and water removal, the effluent gas is analyzed. From this data selectivity is determined to 6 31.9% for methyl acetylene and allene. While these ows are held constant, HBr is introduced at a molar atio of 0.078 mole of HBr per mole of propylene. The :mperature is determined to be 1100 C. The resulting 8 selectivity was determined to be 73.4 percent.
  • T role ratio is then 1ncreased to 0.117 mole of 1-IBr per Component: M01e percent nole of propylene.
  • the temperature is 1085 C. and the Hydrogen 7 17 onversion is 51.6%.
  • the selectivity as determined by Oxygen n 2 47 xit gas analysis is 42.8%.
  • the HBr mole ratio 10 Nitronen' n 035 s increased to 0.526 mole HBr per mole of propylene, and Methgne 4O 88 he conversion is 52.0%.
  • the mole ratio of steam to isobutylene and isobutylene to hydrogen bromide are 9 to 1, and 1.57 to 1 respectively.
  • the total reactor pressure is kept at about one atmosphere during the reaction and a thremocouple in the mid- ⁇ dlfi of the cracking tube registers a temperature of 995 C. and the exit temperature from the pyrolysis tube is 902 C.
  • the isobutylene is added after being preheated to a temperature of 200 C.
  • the contact time of reaction as determined by the effective temperature is about 0.0015 second and the resulting isobutylene conversion is 74.6 percent.
  • a water quench is used immediately following the reaction zone and after steam condensation and water removal, the efiluent gas is analyzed. From this data,
  • An isobutylene feed stream is metered and then preheated before being introduced into a stainless steel tube of the same dimensions as previously .given in Example 4 above. Measured quantities of superheated steam and isobutylene are intimately mixed just prior to the reactor tube entrance. The mole ratio of steam to isobutylene is 10 to 1. The temperature in the reactor tube is about 1020 C. The contact time is determined to about .0013 second. The resulting isob-utylene conversion is 80.2 percent and selectivity for methyl acetylene and allene is 38.6 percent 138 determined by analysis of the exit gas.
  • HBr is added at a molar ratio of 11.8 moles of isobiutylene feed to 1 mole of HBr.
  • the temperature is determined to 75 be about 1020 C.
  • the resulting conversion is 85.8 percent and selectivity rose to 46.4 percent as determined by effect of intermediate quantities of hydroben bromide analysis of the exit reactor gas.
  • the ratio of HBr to are shown. Conditions were used and results obtained isobutylene is then increased to 7.55 moles of isobutylene as shown.
  • the ratio of HBr to isofrom propylene which comprises subjecting a mixture of butylene is increased to 0.9 moles of isobutylene per propylene and hydrogen bromide or a bromide containmole of HBr.
  • Analysis of the exit gas revealed that a ing material capable of yielding hydrogen bromide at conversion of 94.1 percent and a selectivity of methyl the reaction conditions, the mole ratio of propylene to acetylene and allene of 55.5 percent is obtained.
  • This hydrogen bromide being from 1 to 1 to 15 to 1, to a temseries of runs very clearly points up the improvement obperature of above 900 C. for from about 0.0005 to 0.01 tained by HBr addition into the cracking zone.
  • the mole reaction conditions, the mole ratio of isobutylene to hyratio of steam to isobutylene is 10 to 1.
  • the temperature drogen bromide being from 1 to 1 to 15 to 1 t a t in the reactor tube is about 975 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US263189A 1963-03-06 1963-03-06 Process for cracking propylene and isobutylene in the presence of hbr Expired - Lifetime US3315004A (en)

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Application Number Priority Date Filing Date Title
GB1051772D GB1051772A (xx) 1963-03-06
US263189A US3315004A (en) 1963-03-06 1963-03-06 Process for cracking propylene and isobutylene in the presence of hbr
DE19641468409 DE1468409A1 (de) 1963-03-06 1964-02-20 Verfahren zur Herstellung von Allen und Methylacetylen
LU45479A LU45479A1 (xx) 1963-03-06 1964-02-20
BE644185D BE644185A (xx) 1963-03-06 1964-02-21
AT155264A AT250317B (de) 1963-03-06 1964-02-24 Verfahren und Herstellung von Allen und Methylacetylen
NL6401710A NL6401710A (xx) 1963-03-06 1964-02-24

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US263189A US3315004A (en) 1963-03-06 1963-03-06 Process for cracking propylene and isobutylene in the presence of hbr

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AT (1) AT250317B (xx)
BE (1) BE644185A (xx)
DE (1) DE1468409A1 (xx)
GB (1) GB1051772A (xx)
LU (1) LU45479A1 (xx)
NL (1) NL6401710A (xx)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454667A (en) * 1965-07-23 1969-07-08 Chiyoda Chem Eng Construct Co Method of producing methyl acetylene and allene from propylene

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2370513A (en) * 1942-02-28 1945-02-27 Dow Chemical Co Production of conjugated diolefins
US2397638A (en) * 1943-03-27 1946-04-02 Pure Oil Co Conversion of hydrocarbons
US2429566A (en) * 1942-04-01 1947-10-21 Francis O Rice Cracking of olefins
US2763703A (en) * 1952-09-29 1956-09-18 Happel John Cracking of isobutylene with steam to produce substituted acetylenes and diolefins
GB807149A (en) * 1956-07-30 1959-01-07 Bataafsche Petroleum Dehydrogenation process
US2925451A (en) * 1957-03-20 1960-02-16 Du Pont Conversion of propylene and isobutylene to allene and methylacetylene
GB868566A (en) * 1959-03-30 1961-05-17 Goodyear Tire & Rubber Cracking of olefins
GB915447A (en) * 1960-09-29 1963-01-09 Goodyear Tire & Rubber Cracking promoters
US3082273A (en) * 1959-12-04 1963-03-19 Tno Process for the production of unsaturated hydrocarbons with three carbon atoms
US3207806A (en) * 1960-11-23 1965-09-21 Petro Tex Chem Corp Dehydrogenation process

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2370513A (en) * 1942-02-28 1945-02-27 Dow Chemical Co Production of conjugated diolefins
US2429566A (en) * 1942-04-01 1947-10-21 Francis O Rice Cracking of olefins
US2397638A (en) * 1943-03-27 1946-04-02 Pure Oil Co Conversion of hydrocarbons
US2763703A (en) * 1952-09-29 1956-09-18 Happel John Cracking of isobutylene with steam to produce substituted acetylenes and diolefins
GB807149A (en) * 1956-07-30 1959-01-07 Bataafsche Petroleum Dehydrogenation process
US2925451A (en) * 1957-03-20 1960-02-16 Du Pont Conversion of propylene and isobutylene to allene and methylacetylene
GB868566A (en) * 1959-03-30 1961-05-17 Goodyear Tire & Rubber Cracking of olefins
US3082273A (en) * 1959-12-04 1963-03-19 Tno Process for the production of unsaturated hydrocarbons with three carbon atoms
GB915447A (en) * 1960-09-29 1963-01-09 Goodyear Tire & Rubber Cracking promoters
US3207806A (en) * 1960-11-23 1965-09-21 Petro Tex Chem Corp Dehydrogenation process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3454667A (en) * 1965-07-23 1969-07-08 Chiyoda Chem Eng Construct Co Method of producing methyl acetylene and allene from propylene

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NL6401710A (xx) 1964-09-07
DE1468409A1 (de) 1969-10-23
BE644185A (xx) 1964-08-21
LU45479A1 (xx) 1964-04-20
AT250317B (de) 1966-11-10
GB1051772A (xx)

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