US2825740A - Production of acetic acid - Google Patents
Production of acetic acid Download PDFInfo
- Publication number
- US2825740A US2825740A US459807A US45980754A US2825740A US 2825740 A US2825740 A US 2825740A US 459807 A US459807 A US 459807A US 45980754 A US45980754 A US 45980754A US 2825740 A US2825740 A US 2825740A
- Authority
- US
- United States
- Prior art keywords
- acetic acid
- oxidation
- weight
- oxygen
- per hour
- 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
Links
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 33
- 229930195733 hydrocarbon Natural products 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 21
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011541 reaction mixture Substances 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010924 continuous production Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 10
- 238000004821 distillation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000228957 Ferula foetida Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 241001208007 Procas Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
Definitions
- the present invention relates to improvements in a process for the production of acetic acid by the liquid phase oxidation with molecular oxygen of paraflinic hydrocarbons containing 4-8 carbon atoms.
- the process for the production of acetic acid comprises oxidising parafiin hydrocarbons of 4-8 carbon atoms in the liquid phase at a temperature in the range 150-220 C. with molecular oxygen continuously withdrawing part of the reaction mixture and passing it to a distillation zone, distilling said part to remove as distillate the material boiling in the presence of water up to 99 C., and returning this distillate with the fresh hydrocarbon feed to the oxidation zone, the throughput rates of the oxygen and the hydrocarbons being such that the ratio, hereinafter termed A, of the weight of oxygen taken up per hour to the weight of the fresh hydrocarbon fed plus the weight of the distillate returned to the oxidation zone per hour is at least 0.5 and recovering acetic acid from the residues of the distillation.
- the ratio A varies with the residence time per pass and/or the oxygen uptake rate, shorter residence times (i. e. faster total feed rates to the oxidation zone) or lower oxygen uptake rates leading to lower values for A.
- A can be controlled from a figure approaching zero to a figure of about 1.0, simply by adjustments of the total feed rate to t.e oxidation zone, and of the air (or oxygen) rate through the oxidation zone.
- the withdrawal of the reaction mixture from the oxidation zone may be carried out in any suitable way. It has been found that the reaction mixture is normally a homogeneous liquid at operating temperature, but that on cooling two liquid layers separate. Of these the upper layer is composed mainly of unchanged hydrocarbon, while the lower layer contains the bulk of the acidic products and water. it is preferred to operate by removing continuously or intermittently a part of the reaction mixture as a homogeneous liquid, to cool this to a temperature below about 80 C. and preferably to as near room temperature as may be convenient, to separate the liquid layers, to return the upper layer without treatment to the oxidation zone and to pass the lower aqueous layer or a part thereof to the distillation zone, which may consist of one or more distillation stages. According to a preferred embodiment of the invention the ratio, hereinafter termed B, of the weight of the distillate returned to the oxidation zone per hour to the weight of the lower aqueous layer passed to the distillation zone per hour is not greater than 0.55.
- the parafiin hydrocarbon or mixture of hydrocarbons of four to eight carbon atoms employed for the oxidation is desirably one which does not exert too high a mixture is maintained 2 vapour pressure, specifically those which are normally liquid at room temperatures of about 30 C. and atmospheric pressure, such as normal pentane and the C to C parafiins, and mixtures thereof.
- the oxidation may be effected with any gas containing molecular oxygen, Whether in the form of air or of mixtures poorer or richer in oxygen than is air; part of the molecular oxygen may, if desired, be in the form of ozone.
- the temperature of oxidation should be sufiiciently high to provide an economically attractive rate of oxidation and a low level of peroxidic compounds.
- the temperature should not be so low that insufiicient oxidation to acids occurs or alternatively be so high that excessive oxidation occurs of the hydrocarbons, or of their primary oxidation products, to oxides of carbon and water.
- Temperatures in the range about C. to 200 C. are preferred, although it is also possible to use higher or lower temperatures.
- the oxidation may be carried out in a variety of types of apparatus, provided only that the reaction substantially in the liquid phase, and that adequate contacting is effected between the liquid reaction mixture and the oxidising gas.
- the oxidation may be carried out in a reactor in the form of a vertical tower with the feed of oxidising gas at the base, or at a number of points up the tower, in which case the necessary agitation is efiected by the gas itself; this case it is advantageous to subdivide the gas feed by mechanical means to obtain a fine dispersion at the point or points of entry and throughout the reaction zone.
- the oxidising gas may be fed into a stream of liquid moving with high velocity in a circulatory system, such as a coil reactor with forced circulation, whereby turbulent conditions of flow are obtained.
- a circulatory system such as a coil reactor with forced circulation
- Other types of apparatus and means for efi'ecting the agitation intermixing of the reactants may also be used.
- oxidations may be carried out in the absence of any added catalyst, or in the presence of a suitable oxidation catalyst.
- a suitable oxidation catalyst include compounds of those metals that are capable of existing in more than one valency state.
- suitable metals include manganese, cobalt, nickel, vanadium and copper.
- These catalysts may be conveniently added in the form of their oil-soluble salts with organic acids, or alternatively the catalyst metal may be added in the form of an anion, whether as the free acid or a salt thereof for example as a vanadate.
- the acetic acid may then be recovered by any suitable method, for instance by azeotropic drying of the wet acids followed by fractional distillation.
- Example 1 hing, and recycled to the oxidation reactor.
- Fresh hydrocarbon is introduced continuously by line 3 through a preheater 13. Both gaseous and liquid reaction products are removed from the reactor by line 4, and after cooling in cooler 5 are fed to gas/liquid separator 6,'from which the waste gases are withdrawn by line 7. Small amounts of hydrocarbon in the waste gas may be recovered in part by suitable means, for example by oil scrub The cooled liquid products pass to liquid/liquid separator 3, Where the aqueous acid product phase is allowed to settle as a lower layer, part of this layerbeing withdrawn as product through line 9. . The upper hydrocarbon layer is returnedto the reactor through preheater it with the remainder of the separated lower layer.
- the whole of the withdrawn aqueous acid product is fed by line'9 through a preheater (not shown) to the mid-point of a packed continuous distillation column 11 which has the equivalent of 5 theoretical plates above and below the feed point.
- the column is operated at atmospheric pressure with a reflux ratio of 4:1, the temperatures being approximately 66- C. at the head, approximately 82 C. at the feed point, and 104-105 C. in the reboiler the distillate passes from the top of the still to a cooler 15 and a separator 16.
- the total distillate minus reflux is returned by line '12 to the oxidation reactor after admixture with'the fresh hydrocarbon feed.
- the base product from the still is withdrawn by line 14, and submitted to further distillation processes to recover the acids formed as main product.
- the product comprising acids of l4 carbon atoms contained 74.3% acetic acid.
- Example 2 An oxidation was carried out in'the same equipment as described in Example 1, using the same feedstock, but under the following conditions; 7 Temperature: 200 C. Pressure: 600 lbs. per .square inch :gauge.
- Oxygen uptake (absorption) rate 816 grams per hour
- Product withdrawal rate feed rate to 11:1 grams per hour.
- the product comprising acids of 1-4 carbon atoms contained 77.9% acetic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2825740X | 1953-10-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2825740A true US2825740A (en) | 1958-03-04 |
Family
ID=10916014
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US459807A Expired - Lifetime US2825740A (en) | 1953-10-07 | 1954-10-01 | Production of acetic acid |
Country Status (2)
Country | Link |
---|---|
US (1) | US2825740A (fr) |
FR (1) | FR1108672A (fr) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3196182A (en) * | 1962-05-18 | 1965-07-20 | Union Carbide Corp | Oxidation of hydrocarbons |
US3247249A (en) * | 1962-07-09 | 1966-04-19 | Halcon International Inc | Preparation of formic and acetic acids by oxidizing methylcyclohexane or paraffin wax in the presence of manganese bromide |
US3271447A (en) * | 1964-05-11 | 1966-09-06 | Du Pont | Liquid phase oxidation of propylene to acrylic acid in the presence of an mn or ni catalyst |
US3282994A (en) * | 1962-07-03 | 1966-11-01 | Union Carbide Corp | Oxidation of butane |
US3335160A (en) * | 1961-04-19 | 1967-08-08 | Knapsack Ag | Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation |
US3337619A (en) * | 1964-02-12 | 1967-08-22 | Monsanto Co | Production of acetic acid and recovery by plural stage distillation |
US3483250A (en) * | 1966-07-08 | 1969-12-09 | Halcon International Inc | Oxidation of n-butane |
EP0546677A1 (fr) * | 1991-12-09 | 1993-06-16 | The Standard Oil Company | Procédé pour oxyder l'éthane en acide acétique dans un lit fluidisé |
US5710318A (en) * | 1994-06-02 | 1998-01-20 | The Standard Oil Company | Fluid bed process for the acetoxylation of ethylene in the production of vinyl acetate |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2452326A (en) * | 1943-01-30 | 1948-10-26 | Shell Dev | Controlled oxidation of paraffinic hydrocarbons |
US2474334A (en) * | 1947-04-10 | 1949-06-28 | Standard Oil Dev Co | Producing maleic acid by oxidation of cyclohexane |
US2653962A (en) * | 1951-07-28 | 1953-09-29 | Celanese Corp | Oxidation control |
US2725344A (en) * | 1952-09-11 | 1955-11-29 | Exxon Research Engineering Co | Upgrading of naphthas |
US2734067A (en) * | 1956-02-07 | Hydrocarbon oxidation |
-
1954
- 1954-09-30 FR FR1108672D patent/FR1108672A/fr not_active Expired
- 1954-10-01 US US459807A patent/US2825740A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2734067A (en) * | 1956-02-07 | Hydrocarbon oxidation | ||
US2452326A (en) * | 1943-01-30 | 1948-10-26 | Shell Dev | Controlled oxidation of paraffinic hydrocarbons |
US2474334A (en) * | 1947-04-10 | 1949-06-28 | Standard Oil Dev Co | Producing maleic acid by oxidation of cyclohexane |
US2653962A (en) * | 1951-07-28 | 1953-09-29 | Celanese Corp | Oxidation control |
US2725344A (en) * | 1952-09-11 | 1955-11-29 | Exxon Research Engineering Co | Upgrading of naphthas |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3335160A (en) * | 1961-04-19 | 1967-08-08 | Knapsack Ag | Process for the continuous manufacture of substantially acetic acidcontaining mixtures of low molecular weight fatty acids by paraffin oxidation |
US3196182A (en) * | 1962-05-18 | 1965-07-20 | Union Carbide Corp | Oxidation of hydrocarbons |
US3282994A (en) * | 1962-07-03 | 1966-11-01 | Union Carbide Corp | Oxidation of butane |
US3247249A (en) * | 1962-07-09 | 1966-04-19 | Halcon International Inc | Preparation of formic and acetic acids by oxidizing methylcyclohexane or paraffin wax in the presence of manganese bromide |
US3337619A (en) * | 1964-02-12 | 1967-08-22 | Monsanto Co | Production of acetic acid and recovery by plural stage distillation |
US3271447A (en) * | 1964-05-11 | 1966-09-06 | Du Pont | Liquid phase oxidation of propylene to acrylic acid in the presence of an mn or ni catalyst |
US3483250A (en) * | 1966-07-08 | 1969-12-09 | Halcon International Inc | Oxidation of n-butane |
EP0546677A1 (fr) * | 1991-12-09 | 1993-06-16 | The Standard Oil Company | Procédé pour oxyder l'éthane en acide acétique dans un lit fluidisé |
US5710318A (en) * | 1994-06-02 | 1998-01-20 | The Standard Oil Company | Fluid bed process for the acetoxylation of ethylene in the production of vinyl acetate |
Also Published As
Publication number | Publication date |
---|---|
FR1108672A (fr) | 1956-01-16 |
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