US3696160A - Selective hydrogenation of diolefins - Google Patents

Selective hydrogenation of diolefins Download PDF

Info

Publication number
US3696160A
US3696160A US22792A US3696160DA US3696160A US 3696160 A US3696160 A US 3696160A US 22792 A US22792 A US 22792A US 3696160D A US3696160D A US 3696160DA US 3696160 A US3696160 A US 3696160A
Authority
US
United States
Prior art keywords
diolefins
percent
butadiene
diolefin
feed
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
US22792A
Inventor
Karl D Chomyn
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
Exxon Research and Engineering Co
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 Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Application granted granted Critical
Publication of US3696160A publication Critical patent/US3696160A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C07C2523/85—Chromium, molybdenum or tungsten
    • C07C2523/888—Tungsten

Definitions

  • ABSTRACT [52] US. Cl ..260/677 H, 260/683.9, 208/255 Diolefins, present in minor amounts, in gaseous feed [51] Int. Cl ..C07c 5/06 streams, particularly those to be used in alkylation [58] Field of Search ..260/677 H, 683.9; 208/255 4 reactions are selectively converted to mono-olefins by hydrogenation over sulfided nickel-tungsten catalyst.
  • This invention relates to the selective hydrogenation of diolefins in hydrocarbon streams containing monoolefins and is especially concerned withselective conversion of propadiene and butadiene contaminants in propylene and butene charge stocks employed in alkylation process for the production of aviation and motor gasoline wherein the feed stock is contaminated with sulfur. It is also useful for the selective conversion of C diolefins to mono-olefins, e.g. butadienes to butenes.
  • the C;,/ C, fraction employed in alkylation processes is principally that obtained from thermal or catalytic cracking of higher boiling hydrocarbons or from a hydrocarbon coking operation; the C l C cut is taken over a practical boiling range so as to be substantially free of C hydrocarbons, although minor amounts of these may be present by entrainment or otherwise.
  • Such C l C fraction may generally contain in the order of about 0.3 percent and up to about 2 percent or more by weight of diolefin; the C;,/ C, fraction from a cracking operation rarely contains as much as 2 percent of diolefin.
  • the selective conversion of diolefins to olefins, particularly in feed stocks containing sulfur is accomplished by effecting the hydrogenation over a catalyst comprising sulfided nickel-tungsten on an inert support such as alumina, kieselguhr, silica-free clay, bauxite, mullite, etc., alumina being preferred.
  • a catalyst comprising sulfided nickel-tungsten on an inert support such as alumina, kieselguhr, silica-free clay, bauxite, mullite, etc., alumina being preferred.
  • the process of the invention involves passing a hydrocarbon stream containing minor amounts of diolefins and sulfur over a sulfided nickel-tungsten catalyst on alumina or other support.
  • a C l C stream is of particular interest in this connection.
  • the catalyst contains 4 to 6 wt. percent nickel, 14 to 20 wt. percent tungsten and the balance A1 0
  • the tungsten to nickel ratio is preferably 4/1 to 5/1.
  • the catalyst is sulfided with H 8 or CS to prior to use.
  • the above catalyst has been found to have a remarkable degree of selectivity in that it is active for the hydrogenation of diolefins to monoolefins but relatively inactive for the hydrogenation of mono-olefins to paraffins in the temperature range of 200400 F pressure -200 psig and hydrogen/diolefin ratio of Hi to 6.1.
  • a further application of the invention lies in the treatment of a butylene-rich stream from a dehydrogenation process containing from a fraction of a percent up to about 5 percent diolefin.
  • butadiene for production of butadiene, particularly after separation of the product butadiene by fractionation and extraction, there still remains in the monoolefin-rich raffinate a small percentage of butadiene of from about a fraction of a percent up to about 2 percent depending upon the efficiency of the separation.
  • This small amount of butadiene cannot be economically recovered as such, and interferes with the possible uses of the raffinate, for instance as feed to alkylation.
  • Some butadiene is also produced in those processes designed principally for conversion of butane to butene. If the quantity of butadiene in the product is sufficiently great, say in excess of about 5 percent its recovery by known procedures may be warranted.
  • the selective hydrogenation of propadiene/butadiene in a mono-olefin-rich mixture by the present invention is more easily accomplished and with greatest efficiency when the proportion of diolefin in the mixture is quite low, for example about 2 percent.
  • FIGS. 1 and 2 83g 2 hydrogenation of propadiene and butadiene are shown Total 100.00 100.00 30 in FIGS. 1 and 2, where FIG. 1 is an Arrhenius plot for cumnylsulfifle'wppM 33-57 '(Nmez) the propadiene conversion and P16. 2 for butadiene Molecular Weight 53.8 (Note 2 Specific Gravity 0.572 Note 2 convers1on, the data bemg set forth 1n Tables 11, Ill, and

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)

Abstract

Diolefins, present in minor amounts, in gaseous feed streams, particularly those to be used in alkylation reactions are selectively converted to mono-olefins by hydrogenation over sulfided nickel-tungsten catalyst.

Description

United States Patent Chomyn 51 Oct. 3, 1972 SELECTIVE HYDROGENATION OF 3,472,763 10/ 1969 Cosyns et al ..208/255 DIOLEFINS 3,234,298 2/1966 Langhout et al ..260/677 H 2,595,772 5/1952 Daussat et a]. ..260/683.9 [72] Invent Karl 3,177,159 4/1965 Rodgers et a1 ..260/683.9 [73] Assignee: Esso Research and Engineering Company Primary Examiner-Delbert E. Gantz Assistant Examiner-Veronica OKeefe [22] Filed March 1970 Attomey-Pearlman and Stahl and C. D. Stores [21] Appl. No.: 22,792
1 [57] ABSTRACT [52] US. Cl ..260/677 H, 260/683.9, 208/255 Diolefins, present in minor amounts, in gaseous feed [51] Int. Cl ..C07c 5/06 streams, particularly those to be used in alkylation [58] Field of Search ..260/677 H, 683.9; 208/255 4 reactions are selectively converted to mono-olefins by hydrogenation over sulfided nickel-tungsten catalyst.
[56] References Cited UNITED STATES PATENTS 4 Claim, 2 Drawing Figures P'ATEN'TEDncI 3 1972 3,696,160
sum 1 or 2 REACTION RATE CONSTANT VERSUS lO /T C CONVERSION IOODr- SYMBOL H /DIENE RATIOS I:I o.s4-|.o4
II Q X,
.10 I I I -I v I I l I0.0 no 2.0 13.0 14.0 5.0 16.0 |?.0
INVENTOR.
KARL D. CHOMYN BY FIG. I.
' ATTORNEY PATEN1E1111111 11112 I 3,696,160
SHEET 2 0F 2 REACTION RATE CONSTANT VERSUS lO /T C ==CONVERSION I0.0
SYMBOL 1-1 DIENE RATIOS CI 0.84-1.04 O o |.64- 2.32 O A 4.7-5.75
II II 4 1 INVENTOR.
ATTORNEY BACKGROUND OF THE INVENTION This invention relates to the selective hydrogenation of diolefins in hydrocarbon streams containing monoolefins and is especially concerned withselective conversion of propadiene and butadiene contaminants in propylene and butene charge stocks employed in alkylation process for the production of aviation and motor gasoline wherein the feed stock is contaminated with sulfur. It is also useful for the selective conversion of C diolefins to mono-olefins, e.g. butadienes to butenes.
The C;,/ C, fraction employed in alkylation processes is principally that obtained from thermal or catalytic cracking of higher boiling hydrocarbons or from a hydrocarbon coking operation; the C l C cut is taken over a practical boiling range so as to be substantially free of C hydrocarbons, although minor amounts of these may be present by entrainment or otherwise. Such C l C fraction may generally contain in the order of about 0.3 percent and up to about 2 percent or more by weight of diolefin; the C;,/ C, fraction from a cracking operation rarely contains as much as 2 percent of diolefin. Even this small content of diolefin in the feed for the alkylation process has been widely recognized as being extremely undesirable for the one reason, among others, of the greatly increased consumption of acid made necessary thereby, as a result of forming tarry acid-diolefin condensation products, adversely affecting the over-all economics of the alkylation process. Several suggestions for the conversion or removal of the diolefins from hydrocarbon mixtures also containing monoolefins have not proved attractive, because of accompanying concomitant disproportionate loss of mono-olefins in the treated product, and high operating and investment costs.
In the case of a C C fraction derived from a coking operation which may contain'even higher proportions of diolefins, going up to 5 percent or more, the problem is even more acute, and the use of such fractions for alkylation has been largely avoided.
Among the suggestions made to overcome the above difficulties is the proposal made in US. Pat. No. 3,1 13,983 to Kirsch et al., issued Dec. 10, 1963, wherein diolefin contaminants are selectively hydrogenated to olefins in an alkylation feed by passage of the feed over a sulfided cobalt molybdenum catalyst supported on A1 0 Unfortunately the use of such catalysts has several drawbacks.
l. Relatively high operating severity is required (pressure 200-400 psig, temperatures higher than 400 F.
2. To maintain the catalyst activity at the desired Supported nickel and palladium catalysts are excellent hydrogenation catalysts in the diolefin conversion service. However, they display very low tolerance of sulfur in the fresh diolefin feed. Consequently, their use is limited to sulfur-free feedstocks.
SUMMARY OF THE INVENTION In accordance with the present invention, the selective conversion of diolefins to olefins, particularly in feed stocks containing sulfur, is accomplished by effecting the hydrogenation over a catalyst comprising sulfided nickel-tungsten on an inert support such as alumina, kieselguhr, silica-free clay, bauxite, mullite, etc., alumina being preferred.
DETAILED DESCRIPTION The process of the invention involves passing a hydrocarbon stream containing minor amounts of diolefins and sulfur over a sulfided nickel-tungsten catalyst on alumina or other support. A C l C stream is of particular interest in this connection.
The catalyst contains 4 to 6 wt. percent nickel, 14 to 20 wt. percent tungsten and the balance A1 0 The tungsten to nickel ratio is preferably 4/1 to 5/1. The catalyst is sulfided with H 8 or CS to prior to use.
The above catalyst has been found to have a remarkable degree of selectivity in that it is active for the hydrogenation of diolefins to monoolefins but relatively inactive for the hydrogenation of mono-olefins to paraffins in the temperature range of 200400 F pressure -200 psig and hydrogen/diolefin ratio of Hi to 6.1.
While the greatest advantages of the described process are obtained in the treatment of olefinic C l C hydrocarbon streams containing about 2 percent butadiene by weight of total hydrocarbons, the process is also applicable, but not necessarily with equal results, to the treatment of olefinic C C fractions of higher diolefin content, such as a butane-butylene fraction obtained from a thermal coking operation which may include up to about 5-6 percent diolefins. A further application of the invention lies in the treatment of a butylene-rich stream from a dehydrogenation process containing from a fraction of a percent up to about 5 percent diolefin. For example, in the dehydrogenation of butane, for production of butadiene, particularly after separation of the product butadiene by fractionation and extraction, there still remains in the monoolefin-rich raffinate a small percentage of butadiene of from about a fraction of a percent up to about 2 percent depending upon the efficiency of the separation. This small amount of butadiene cannot be economically recovered as such, and interferes with the possible uses of the raffinate, for instance as feed to alkylation. Some butadiene is also produced in those processes designed principally for conversion of butane to butene. If the quantity of butadiene in the product is sufficiently great, say in excess of about 5 percent its recovery by known procedures may be warranted. Smaller quantities of butadiene, as between about 3 to 5 percent may or may not be worth recovering as such, depending upon recovery costs versus market demand and value. In either of the above instances, the enhancement of the butene product by selective hydrogenation of diolefins in accordance with the present invention, comes into consideration.
The selective hydrogenation of propadiene/butadiene in a mono-olefin-rich mixture by the present invention is more easily accomplished and with greatest efficiency when the proportion of diolefin in the mixture is quite low, for example about 2 percent. In such instance catalytic hydrogenation under the described SPaWfVCIOCiIILSCFH OfFeeMEX- 01 [000 N cu. t. cata yst etc 1) operatmg conditions can be accomphshed 1n isother- Gas Ram, Mole Iii/Mole Diem-m 2240/ (Note 2) mal or ad1abat1c reactor systems, and some var1at1on Pressure at Inlet to Preheat Exchanger, psig 175 from the optimum in process variables can be tolerated at the expense of some sacrifice in yield and purity of produpt' Note 1 Some variation in liquid hourly space velocity (LHSV) oc- To illustrate the benefits of the invention, feeds havcurred in lab. The range of LHSV was 2.8-4.0 V/HrJV. ing the following composition Note 2 Hydrogen to diene ratios were varied from 1.0 to 6.0
TABLEI The data were analyzed on the basis of a first order kinetics expression to calculate the constants KC FEED INSPECTIONS and KC, and defined as follows:
Composition, Wt.% Sample 1 (Note 1) Sample 2 (Note 1) Propane 6.46 6.71 K: S[In(1-x)] Propylene 13.24 13.75 n-Butane 22.79 lso-Butane 7.l6 Butene-l 26.30 26.08 I lsobutylene 1.61 1.56 where- Propadiene 1.39 1.46 lsopentane 2.94 2.86 "9" i g' 2% 22? S space velocity and x is the fraction of reactant ClS uenen-Pentane 0,01; 08 converted 1nto product. y B 3 The effects of the operating temperature on the 53,??? 83g 2 hydrogenation of propadiene and butadiene are shown Total 100.00 100.00 30 in FIGS. 1 and 2, where FIG. 1 is an Arrhenius plot for cumnylsulfifle'wppM 33-57 '(Nmez) the propadiene conversion and P16. 2 for butadiene Molecular Weight 53.8 (Note 2 Specific Gravity 0.572 Note 2 convers1on, the data bemg set forth 1n Tables 11, Ill, and
TABLE I[.SUMMARY OF OPERATIONS Catalyst Ni-W 011 A1203, (10 00., 8-14 Mosh c 't' i igs ifm, p.s.i.g 175 175 175 175 175 175 100 170 175 175 105 175 [e1np0r21tur0, F 100 205 257 270 255 270 305 233 300 2140 350 Feed rate, (gas) liters/hr 50.0 53.0 50.7 50.7 53.1 43.4 30.7 40.1 40. 4 55.11 51.1 Feed rate, (liquid) v./l11'./v 3.05 1.15 3. 06 3. 06 3. 73 3.3!) 2. 3. 36 2.81 6.112 3. 0;? Hydrogen feed, 1it0rs/l11'.. .2. 8 7. 8 2.11 7. 8 2. 6 7. 8 2. G 1.3 2. 3 1. 3 2.11 11211115115 ratio 1.77 4.7 1.04 1.0 1.77 5.75 0.31 1.30 1 1 k=l 1-.
i t linhii w, 0. 5115 0.331 1. 13 1.211 3.35 13111111110110, k 0.55 0.381 0.73 0 4 15 3,311 lrodnct analysis, wt. porcunt: I r lmpnnu (i. 11 1 (i. 11. 21 11. 111 11. .11 l'l'opylonu 13.63 14.13 12.02 13.11 13.1! lsohutzult 23.511 23.76 23.31 23. 78 23.1 n-liutanv. 7.25 7.1111 7.45 7.32 7.10 llutunu-l 25.110 .25. 75 26. 53 20.30 21. 1 lsobutylullu 1.88 1.85 1.8.) .811 1.111 1.813 lropadiene 1. 20 1. 27 1). 111 .83 1. 00 (1.14 101101110 2.110 2.74 3.13 .30 2. 35 3.05 011105115 2 0.32 3. 70 0.33 ..00 11. 07 10.3 0141051102 0.20 0.00 0.05 0.00 0.37 0.311 7. 314 1 3-l)utad1cnc 0.81 0. 31 0.75 0.02 0. 0.70 0.33 0. 37
-3: 112 .13; 0 1.1 3' 1,0 1"; s 0.24 0. 1 .2. 40.71 40.05 40.31 50.10 51.40 40.55 51.07 50.1 1110151111 input, liters/h 1.58 1.47 1.35 1.12 1.34 1.13 1.55 1.4 1 1 83313125... 13.7 8.6 34.5 47.5 30.0 40.2 23.0 00. 0 (11010150115 13 0.7 10.4 3 14.4 24.0 10.7 00.5
Note 1 Duplicate analyses.
Note 2 Not determined.
were hydrogenated at various temperatures and under the following constant conditions:

Claims (3)

  1. 2. The process of claim 1 in which the feed stream contains C3 and C4 diolefins.
  2. 3. The process of claim 1 in which the diolefin content of the feed stream is less than 2 percent.
  3. 4. The process of claim 1 in which the tungsten-to-nickel ratio is said catalyst is between about 4/1 to 5/1.
US22792A 1970-03-26 1970-03-26 Selective hydrogenation of diolefins Expired - Lifetime US3696160A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US2279270A 1970-03-26 1970-03-26

Publications (1)

Publication Number Publication Date
US3696160A true US3696160A (en) 1972-10-03

Family

ID=21811476

Family Applications (1)

Application Number Title Priority Date Filing Date
US22792A Expired - Lifetime US3696160A (en) 1970-03-26 1970-03-26 Selective hydrogenation of diolefins

Country Status (6)

Country Link
US (1) US3696160A (en)
JP (1) JPS5020044B1 (en)
CA (1) CA943977A (en)
DE (1) DE2112650A1 (en)
FR (1) FR2087855A5 (en)
GB (1) GB1339615A (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059504A (en) * 1976-07-21 1977-11-22 The Lummus Company Hydrotreating of pyrolysis gasoline
US4110205A (en) * 1976-08-23 1978-08-29 Uop Inc. Process for hydrogenating a coke-forming hydrocarbon distillate
US4520214A (en) * 1984-04-04 1985-05-28 Uop Inc. High selectivity process for dehydrogenation of paraffinic hydrocarbons
US4523045A (en) * 1984-04-04 1985-06-11 Uop Inc. Process for converting paraffins to olefins
US4523048A (en) * 1984-04-04 1985-06-11 Uop Inc. Process for the selective production of alkylbenzenes
US4761509A (en) * 1987-02-24 1988-08-02 Uop Inc. High selectivity process for dehydrogenation of paraffinic hydrocarbons
US4774375A (en) * 1987-12-11 1988-09-27 Uop Inc. HF alkylation and selective hydrogenation process
US6417135B1 (en) 1999-08-27 2002-07-09 Huntsman Petrochemical Corporation Advances in dehydrogenation catalysis
US6469223B2 (en) * 2000-01-04 2002-10-22 Fina Technology, Inc. Selective hydrogenation of dienes
US20030229285A1 (en) * 2002-06-11 2003-12-11 Simpson David Hope Ultrasonic diagnostic micro-vascular imaging
US20070203375A1 (en) * 2002-02-07 2007-08-30 Yuanyi Yang Composite for catalytic distillation and its preparation
CN106381418A (en) * 2016-08-31 2017-02-08 河南师范大学 Preparation method of high-cube texture Ni-10at. percent W alloy base band
CN107267901A (en) * 2017-07-04 2017-10-20 焦作大学 A kind of preparation method of high intensity without ferromagnetism texture Ni W alloy base band
WO2022084238A1 (en) 2020-10-23 2022-04-28 Exxonmobil Chemical Patents Inc. Methods for producing higher alcohols from waste plastic pyrolysis oil and the higher alcohols obtained therefrom
WO2022084433A1 (en) 2020-10-23 2022-04-28 Exxonmobil Chemical Patents Inc. Hydrocarbon fluids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58125738U (en) * 1982-02-19 1983-08-26 トキコ株式会社 disc brake

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2595772A (en) * 1949-12-08 1952-05-06 Standard Oil Dev Co Method of preparing catalysts
US3177159A (en) * 1961-12-27 1965-04-06 Shell Oil Co Hydroisomerization of olefin
US3223652A (en) * 1962-09-05 1965-12-14 Sinclair Research Inc Preparation of iron group metal catalysts
US3234298A (en) * 1960-10-21 1966-02-08 Shell Oil Co Selective hydrogenation
US3472763A (en) * 1965-02-13 1969-10-14 Inst Francais Du Petrole Catalytic hydrogenation of diolefins

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2595772A (en) * 1949-12-08 1952-05-06 Standard Oil Dev Co Method of preparing catalysts
US3234298A (en) * 1960-10-21 1966-02-08 Shell Oil Co Selective hydrogenation
US3177159A (en) * 1961-12-27 1965-04-06 Shell Oil Co Hydroisomerization of olefin
US3223652A (en) * 1962-09-05 1965-12-14 Sinclair Research Inc Preparation of iron group metal catalysts
US3472763A (en) * 1965-02-13 1969-10-14 Inst Francais Du Petrole Catalytic hydrogenation of diolefins

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4059504A (en) * 1976-07-21 1977-11-22 The Lummus Company Hydrotreating of pyrolysis gasoline
US4110205A (en) * 1976-08-23 1978-08-29 Uop Inc. Process for hydrogenating a coke-forming hydrocarbon distillate
US4520214A (en) * 1984-04-04 1985-05-28 Uop Inc. High selectivity process for dehydrogenation of paraffinic hydrocarbons
US4523045A (en) * 1984-04-04 1985-06-11 Uop Inc. Process for converting paraffins to olefins
US4523048A (en) * 1984-04-04 1985-06-11 Uop Inc. Process for the selective production of alkylbenzenes
US4761509A (en) * 1987-02-24 1988-08-02 Uop Inc. High selectivity process for dehydrogenation of paraffinic hydrocarbons
US4774375A (en) * 1987-12-11 1988-09-27 Uop Inc. HF alkylation and selective hydrogenation process
US6700028B2 (en) 1999-08-27 2004-03-02 Huntsman Petrochemical Corporation Advances in dehydrogenation catalysis
US6417135B1 (en) 1999-08-27 2002-07-09 Huntsman Petrochemical Corporation Advances in dehydrogenation catalysis
US6469223B2 (en) * 2000-01-04 2002-10-22 Fina Technology, Inc. Selective hydrogenation of dienes
US20070203375A1 (en) * 2002-02-07 2007-08-30 Yuanyi Yang Composite for catalytic distillation and its preparation
US7642388B2 (en) * 2002-02-07 2010-01-05 China Petroleum & Chemical Corporation Composite for catalytic distillation and its preparation
US20030229285A1 (en) * 2002-06-11 2003-12-11 Simpson David Hope Ultrasonic diagnostic micro-vascular imaging
CN106381418A (en) * 2016-08-31 2017-02-08 河南师范大学 Preparation method of high-cube texture Ni-10at. percent W alloy base band
CN107267901A (en) * 2017-07-04 2017-10-20 焦作大学 A kind of preparation method of high intensity without ferromagnetism texture Ni W alloy base band
WO2022084238A1 (en) 2020-10-23 2022-04-28 Exxonmobil Chemical Patents Inc. Methods for producing higher alcohols from waste plastic pyrolysis oil and the higher alcohols obtained therefrom
WO2022084433A1 (en) 2020-10-23 2022-04-28 Exxonmobil Chemical Patents Inc. Hydrocarbon fluids

Also Published As

Publication number Publication date
GB1339615A (en) 1973-12-05
CA943977A (en) 1974-03-19
DE2112650A1 (en) 1971-10-21
JPS5020044B1 (en) 1975-07-11
FR2087855A5 (en) 1971-12-31

Similar Documents

Publication Publication Date Title
US3696160A (en) Selective hydrogenation of diolefins
US6075173A (en) Process for production of isobutene and propylene from hydrocarbon cuts containing four carbon atoms
US10227279B2 (en) Dehydrogenation of LPG or NGL and flexible utilization of the olefins thus obtained
US6743958B2 (en) Process for selective production of propylene from hydrocarbon fractions with four carbon atoms
US5012021A (en) Process for the production of alkylaromatic hydrocarbons using solid catalysts
US3770619A (en) Process for hydrocarbon purification by selective hydrogenation
US2395875A (en) Dehydrogenation of hydrocarbons
US3781195A (en) Process for the production of gaseous olefins from petroleum distillate feedstocks
US3872180A (en) Method for producing isopentene
SU1349696A3 (en) Method of producing benzol
US20160207848A1 (en) Combined preparation of butene and octene from ethene
US4361422A (en) Hydrogenation and etherification of an unsaturated C5 hydrocarbon cut to increase its octane number and decrease its mono-olefin content
US3767565A (en) Preparation of high octane gasoline using disproportionation, alkylation and dimerization steps
EP0691318B1 (en) Olefin metathesis
US3679773A (en) Dehydrogenation-type reactions with group viii catalysts
US3692863A (en) Dehydrogenation and dehydrocyclization method
US3725493A (en) Oxidative dehydrogenation
US9260386B2 (en) Thioetherification of mercaptanes in C4 hydrocarbon mixtures
US3172834A (en) Process for manufacturing gasoline by blending the hydrocracked gasoline with the dehydrogenated and alkyl- ated products obtained from the hy- drocracking stage
US4761509A (en) High selectivity process for dehydrogenation of paraffinic hydrocarbons
US6548721B1 (en) Hydrotreating olefin stream with complete destruction of oxygenates
US20070043247A1 (en) Diisobutylene production
US4520214A (en) High selectivity process for dehydrogenation of paraffinic hydrocarbons
US3679763A (en) Purification of process gas streams by hydrogenation
US3321545A (en) Olefins by hydrogen transfer