CN1344240A - Methods of extracting catalyst in solution in mfg. adipic acid - Google Patents
Methods of extracting catalyst in solution in mfg. adipic acid Download PDFInfo
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- CN1344240A CN1344240A CN00805435A CN00805435A CN1344240A CN 1344240 A CN1344240 A CN 1344240A CN 00805435 A CN00805435 A CN 00805435A CN 00805435 A CN00805435 A CN 00805435A CN 1344240 A CN1344240 A CN 1344240A
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- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title abstract 6
- 239000001361 adipic acid Substances 0.000 title abstract 3
- 235000011037 adipic acid Nutrition 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 40
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000011541 reaction mixture Substances 0.000 claims abstract description 31
- 239000000284 extract Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 34
- 230000002411 adverse Effects 0.000 claims description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 29
- 238000007254 oxidation reaction Methods 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 15
- 230000006578 abscission Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 150000001408 amides Chemical class 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 abstract 3
- ZRJUCHNILNOEKV-UHFFFAOYSA-N hexan-2-one hydrate Chemical compound O.CCCCC(C)=O ZRJUCHNILNOEKV-UHFFFAOYSA-N 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 18
- 238000000605 extraction Methods 0.000 description 16
- 239000006200 vaporizer Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 238000007599 discharging Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000013473 artificial intelligence Methods 0.000 description 2
- 238000013528 artificial neural network Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- CNWDMHWFOQSFPS-UHFFFAOYSA-N butanedioic acid;cobalt Chemical compound [Co].OC(=O)CCC(O)=O CNWDMHWFOQSFPS-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- XIAAQBHIJXGDQH-UHFFFAOYSA-N cobalt;pentanedioic acid Chemical compound [Co].OC(=O)CCCC(O)=O XIAAQBHIJXGDQH-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000007520 diprotic acids Chemical class 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003809 water extraction Methods 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 hexanaphthene Chemical class 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000020004 porter Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000007306 turnover Effects 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
- C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
This invention relates to methods of extracting in solution a metal catalyst from a reaction mixture produced by oxidizing cyclohexane to adipic acid in the presence of acetic acid and the metal catalyst. According to this invention, substantially the totality of the cyclohexane is removed, as well as a major part of the adipic acid. A major part of the acetic acid is also removed without precipitating catalyst, thus forming a concentrate in solution. In a preferred embodiment of the instant invention, the concentrate enters a counter-current stream of counter flowing water and cyclohexanone, resulting in an aqueous solution of metal catalyst, which is the extract, and a phase of concentrate solution dissolved in cyclohexanone, which is the raffinate. The two solutions are further treated and/or recycled.
Description
Technical field
The present invention relates to cyclohexane oxidation is the method for hexanodioic acid, more specifically, the present invention relates to extract how continuously the catalyzer of solution form, is preferred for recycling.
Background technology
Have various reference (patent documentation and article document) to relate to the formation of acid, most important a kind of be the hexanodioic acid that forms by the hydrocarbon oxidation.Hexanodioic acid is used to produce nylon 66 fiber and resin, polyester, urethane and various other compound.
The method that different production hexanodioic acids is arranged.Usual method comprises that the first step is the mixture (KA mixture) of pimelinketone and hexalin with oxygen with cyclohexane oxidation, is oxidized to hexanodioic acid with nitric acid with the KA mixture then.Other method comprises " hydroperoxide method ", " borate method " and " direct synthesis technique ", and direct synthesis technique is included under the existence of solvent, catalyzer and promotor, is hexanodioic acid with cyclohexane oxidation directly with oxygen.
Direct synthesis technique has been subjected to have paid close attention to for a long time.Yet almost there is not the coml success so far.One of them reason is, and is although it looks very simple, in fact very complicated.Because this complicacy, people can find very result, argumentation and the viewpoint of contradiction in different reference.
Be well known that, according to direct synthesis technique be reflected at carry out after, at room temperature have the mixture of two liquid phases, and a solid phase of mainly forming by hexanodioic acid.Two liquid phases are called " polar phase " and " nonpolar phase ".Yet people do not notice the importance of these two phases all the time, except hexanodioic acid is separated from " polar phase ", and with these mutually partly or entirely, handle or without further looping back in the reactor with handling.
It should be noted that equally most researchs for direct synthesis technique are with intermittent mode, reference literature ground (literally) or carry out for putting into practice the point of destination fully.
As mentioned above, various documents about oxidation of organic compounds relieving haperacidity are arranged, for example hexanodioic acid and/or intermediate product are as pimelinketone, hexalin and cyclohexyl hydroperoxide etc.
About the preparation of diprotic acid and other intermediate oxidation product, wherein following document can be thought the representative of method for oxidation.
United States Patent (USP) 5463119 (Kollar); United States Patent (USP) 5374767 (Drinkard etc.); United States Patent (USP) 5321157 (Kollar); United States Patent (USP) 3987100 (Barnette etc.); United States Patent (USP) 3957876 (Rapoport etc.); United States Patent (USP) 3932513; United States Patent (USP) 3530185 (Pugi); United States Patent (USP) 3515751 (Oberster etc.); United States Patent (USP) 3361806 (Lidov etc.); United States Patent (USP) 3234271 (Barker etc.); United States Patent (USP) 3231608 (Kollar); United States Patent (USP) 3161603 (Leyshon etc.); United States Patent (USP) 2565087 (Porter etc.); United States Patent (USP) 2557282 (Hamblet etc.); United States Patent (USP) 2439513 (Hamblet etc.); United States Patent (USP) 2223494 (Loder etc.); United States Patent (USP) 2223493 (Loder etc.).
German patent DE 4426132 A1 (Kysela etc.) disclose a kind of dewatering of handling acetate from the cyclohexane liquid-phase oxidation that carries out with air, it is in the presence of the cobalt salt as catalyzer, after filtration, isolate and carry out after the hexanodioic acid, in dehydration column, prevent simultaneously the cobalt salt precipitation, it is characterized in that at dephlegmate to the condition of residual content less than [sic] 0.3～0.7%, by using the hexanaphthene that adds, make the acetate that will turn back to the technology starting point carry out component distillation mutually.
It is in the reaction of hexanodioic acid in the hexanaphthene direct oxidation that PCT International Application No. WO 96/03365 (Costantini etc.) and United States Patent (USP) 5756837 (Costantini etc.) disclose a kind of, recovery contains the method for the catalyzer of cobalt, it is characterized in that comprising such step, wherein pentanedioic acid and the Succinic Acid that forms in reaction process by extraction at least a portion handled by being oxidized to the reaction mixture that hexanodioic acid obtains.
In the document known to above-mentioned document or any other inventor, none is separately or in combination open or hinted that with the as described below and complexity of the present invention that requires and Critical Control and requirement be condition, the controlled oxidation reaction.
Summary of the invention
As mentioned above, the present invention relates to a kind of with hydro carbons such as hexanaphthene, be oxidized to separately intermediate oxidation product such as the method for hexanodioic acid, more specifically, the present invention relates to extract how continuously the catalyzer in the solution, be preferred for recycling.More specifically, the present invention relates to a kind of method of extracting metal catalyst from reaction mixture with the solution form, by being that hexanodioic acid makes with cyclohexane oxidation, this method comprises the steps: described reaction mixture in the presence of acetate and metal catalyst
(a) remove whole hexanaphthenes basically;
(b) remove the hexanodioic acid of major portion;
(c) remove the acetate (go up to basically 100%) of major portion, but make with being careful be no more than when removing acetate catalyzer begin sedimentary that, form the solution concentration thing thus;
(d) described enriched material is incorporated into the region intermediate of an adverse current logistics, this adverse current logistics also has a bottom section and a upper area, and bottom section has the bottom, and upper area has the top;
(e) pimelinketone that can contain less water is incorporated into the bottom section of described adverse current logistics;
(f) water that can contain a small amount of pimelinketone is incorporated into the upper area of described adverse current logistics;
(g) take out first liquid or raffinate from the top of upper area, this first liquid contains the enriched material of the major portion except that catalyzer; And
(h) take out second liquid or extract from the bottom of bottom section, this second liquid contains the metal catalyst of major portion.
The preferable alloy catalyzer is the compound that contains cobalt.Metal catalyst is essentially metal itself, is preferably ionic species, and does not consider compound associating with it or part.Thus, metal can associate with a part in step (a), and associates with another distinct portions in step (h); For example, it can mainly be a cobaltous acetate in step (a), and it can mainly be the hexanodioic acid cobalt in step (h), or pentanedioic acid cobalt or Succinic Acid cobalt, or any their mixture.
Can be before removing hexanodioic acid, in its process or remove hexanaphthene afterwards, perhaps before removing hexanodioic acid and remove hexanaphthene afterwards.Before or after be meant process early or late phase, and be meant in the process in the identical stage.For example, remove hexanaphthene and can form two different liquid phases by reducing temperature and making, promptly nonpolar phase contains the hexanaphthene of major portion, and polar phase contains acetate, hexanodioic acid and other polarity part of major portion, remove nonpolar phase by decantation subsequently, and hexanodioic acid is removed in crystallization.Another selectable method is to remove hexanaphthene in the flash crystallization process of hexanodioic acid.Can also remove hexanaphthene by distillation.
Particularly preferably be step (d), (e), (f), (g) and (h) carry out simultaneously.And step (c) is preferably undertaken by distillation.Can be continuously in step (c) or add less water off and on.
Also particularly preferably be, in step (c), remove whole basically acetate, and in step (h), take out whole basically metal catalysts.
Basically removing fully under the situation of catalyzer at needs, in the adverse current stream portions, is absolute important as keeping sufficiently high temperature in the top end part of the adverse current logistics that only has little amount of catalyst, its objective is to reduce or eliminate the emulsive tendency.
The temperature of top, centre and base section can be substantially the same; Preferred range is 50～80 ℃.
Yet more preferably, the temperature at top is higher than the temperature of middle portion, and the temperature of middle portion is higher than the temperature of bottom.Further more preferably, the temperature range at top is 50～90 ℃, and the temperature range of middle portion is 30～50 ℃, and the temperature range of bottom is 10～40 ℃.
The invention still further relates to a kind of method of extracting metal catalyst from reaction mixture with the solution form, wherein said reaction mixture is in the presence of acetate and metal catalyst, and by what cyclohexane oxidation to hexanodioic acid was made, this method comprises the steps:
(k) remove whole hexanaphthenes basically;
(l) remove the hexanodioic acid of major portion;
(m) not making the acetate of removing major portion under the catalyst precipitation, form the solution concentration thing thus;
(n) described enriched material is incorporated into intermediate stage of an adverse current multistage device, this intermediate stage comprises a middle mixing zone and an intermediate section abscission zone, this adverse current multistage device also comprises an anterior stage and a rear portion stage, the anterior stage comprises an anterior mixing zone and a fore portion abscission zone, and the rear portion stage comprises mixing zone, a rear portion and abscission zone, a rear section;
(p) pimelinketone that can contain less water is incorporated into described anterior mixing zone;
(q) water that can contain a small amount of pimelinketone is incorporated into mixing zone, described rear portion;
(r) take out raffinate from the abscission zone, rear section, this raffinate contains the enriched material of the major portion except that catalyzer; And
(s) take out extract from the fore portion abscission zone, this extract contains the metal catalyst of major portion.
Preferred steps (m) is undertaken by distillation, and this method also can further comprise the step that adds entry in step (m) in this case.
At least in abscission zone, described rear section, can separate by centrifugation step at least in part.
In one embodiment of the invention, the rear portion stage has a rear portion phase temperature, and the intermediate stage has an intermediate stage temperature, and the anterior stage has an anterior phase temperature; Rear portion phase temperature, intermediate stage temperature and anterior phase temperature are identical basically.Preferably, this substantially the same temperature range is 50～80 ℃.
In a different embodiment, the temperature in rear portion stage is higher than the temperature in intermediate stage, and the temperature in intermediate stage is higher than the temperature in anterior stage.Preferably, the temperature range in rear portion stage is 50～90 ℃, and the temperature range in intermediate stage is 30～50 ℃, and the temperature range in anterior stage is 10～40 ℃.
According to the present invention, preferred whole basically acetate is removed in step (m).Also preferred whole basically metal catalyst is removed in step (s).
As mentioned above, metal catalyst is preferably a kind of compound that contains cobalt.Metal catalyst is essentially metal itself, is preferably ionic species, and does not consider compound associating with it or part.Thus, metal can associate with a part in step (k), and associates with another distinct portions in step (s); For example, it can mainly be a cobaltous acetate in step (k), and it can mainly be the hexanodioic acid cobalt in step (s), or pentanedioic acid cobalt or Succinic Acid cobalt, or any their mixture.
Special preferred steps (n), (p), (q), (r) and (s) carry out simultaneously.And step (m) is preferably undertaken by distillation.Can be continuously in step (m) or add less water off and on, to keep the solvability of metal catalyst.
Method of the present invention also can further comprise in some way with hexanodioic acid that makes and the step that is selected from a kind of reactant reaction of polyvalent alcohol, polyamine and polynary acid amides, to form polyester or polymeric amide or (polyimide and/or polyamidoimide) polymkeric substance respectively, these polymkeric substance can further be spun to fiber, or mix to form matrix material with filler and/or other additive.
" main " and relate to the part of " major portion ", be meant described part weight more than 50%, and go up to basically 100%.
" a spot of " and relate to the part of " small portion ", be meant described part weight less than 50%, and down to 0%.
" phase on top " is meant " the less hexanaphthene phase of relative polarity that contains little amount of catalyst ", and " phase of bottom " is meant " the bigger water of relative polarity that contains main catalyzer ".For for simplicity, this explanation be not only applicable to produce the top loop hexanone mutually and the separator of lower aqueous be the situation of decantor, but also be applicable to that separator is the situation of centrifuge separator.
Any stage in anterior stage of " intermediate stage " right and wrong and rear portion stage.
Description of drawings
By in conjunction with reference to following detailed description and accompanying drawing, will deepen the understanding of the present invention, wherein:
Fig. 1 is the block diagram of a preferred embodiment of the present invention, wherein carries out the extraction of catalyzer in the adverse current logistics.
Fig. 2 is the block diagram of another preferred embodiment of the present invention, wherein carries out the extraction of catalyzer in the multistage extraction element.
The preferred forms of invention
As mentioned above, the present invention relates to for example cyclohexane oxidation is the method and apparatus of hexanodioic acid, more specifically, the present invention relates to how to extract catalyzer with the solution form after reaction, is preferred for recycling.
Suitably handle catalyzer in oxidizing reaction is the problem that merits attention in this area always.According to the present invention, being dissolved in the liquid form separating catalyst of aqueous phase, and preferably after the processing of carrying out and do not carry out other, it is sent back in the reaction chamber.
The inventor finds, after cyclohexane oxidation being hexanodioic acid with required transformation efficiency, and after removing the hexanodioic acid of major portion, remaining hexanaphthene and water and main at least acetate, reaction mixture can be before pimelinketone that adds critical amount and water and afterwards, obtains or be retained as no solid single-phase liquid.The water of available additional quantity perhaps reduces by temperature and extracts catalyzer then, and preferably after the processing of carrying out and do not carry out other it is sent back in the reaction chamber.
According to the present invention, will improve the separation method of catalyzer widely by using following technology:
With reference now to Fig. 1,, what illustrate among the figure is a catalyst separating unit 10 that comprises vaporizer or distiller 12, and wherein vaporizer or distiller 12 are connected on the region intermediate 19 of a complex compound counter-current extraction tower 14 by line of pipes 16.Complex compound counter-current extraction tower 14 comprises complex compound extraction zone 18.Except that region intermediate 19, tower 14 also has bottom section 20 and upper area 22.Bottom section 20 has a bottom 24, and upper area 22 has a top 26.Water pipeline 28 and pimelinketone pipeline 30 are connected on the complex compound counter-current extraction tower 14, and tower 14 is connected with enriched material solution pipeline or raffinate pipeline 34 with catalyst solution pipeline or extract pipeline 32 again.
Vaporizer or distiller 12 are connected on the vapor line 15, and optional simultaneously charge line 13 and the reaction mixture pipeline of handling 11 are connected on the vaporizer 12.Well heater or interchanger 17 are parts of vaporizer 12.
The equipment of 10 front and backs, catalyst separating unit do not show in Fig. 1 because they at length we patent and application in described, these patents and application are drawn be reference here.
In the operation of this embodiment, make from cyclohexane oxidation be the processing that comes of hexanodioic acid reaction mixture (as we patent and co-pending application described in, here they are incorporated herein by reference) enter into vaporizer or distiller 12 by pipeline 11.The mixture of handling is to remove remaining mixture behind the hexanodioic acid of major portion at least from reaction mixture, and above-mentioned reaction mixture is at acetate and metal catalyst, and preferred cobalt compound exists down, by being that hexanodioic acid makes with cyclohexane oxidation.The reaction mixture of handling can contain main or a spot of unreacted hexanaphthene.Can by reaction mixture is separated into (i) contain major portion acetate, hexanodioic acid, other polarity part and catalyzer polar phase and (ii) contain the nonpolar phase of the hexanaphthene of major portion, and remove hexanaphthene.Under such situation, recyclable nonpolar phase simultaneously can be by carrying out the hexanodioic acid that major portion is removed in crystallization from polar phase.Under this situation, after removing hexanodioic acid, residuum has constituted the reaction mixture of handling.Under another different situation, can remove hexanaphthene major portion or a spot of by the flash crystallization that carries out hexanodioic acid simultaneously.Under this situation, after removing hexanodioic acid, residuum has constituted the reaction mixture of handling.
Although it is in demand removing hexanaphthene before the reaction mixture of handling enters vaporizer or distiller 12, optional, recognize that this point is crucial.
The acetate of the major portion by evaporating existence is concentrated into a required degree with the reaction mixture that enters the processing of vaporizer 12.It is apparent that because its higher volatility, the hexanaphthene of any existence and most water will be by pipeline 15 evaporations, even before the acetate evaporation.It is highly important that, will leave away with the form of liquid by pipeline 16 by the enriched material that the acetate that evaporates major portion makes, even these liquid viscosity, but but still pumping.
In the process of evaporation of acetic acid, can add a spot of water continuously or off and on by charge line 13.Adding entry is important for the amount of acetate is minimized, and purpose is the factors such as relative quantity according to compound in transformation efficiency and the enriched material, and keeping enriched material is no solid form.
Enriched material enters the complex compound extraction zone 18 of complex compound counter-current extraction tower 14, wherein has adverse current logistics 18 ＇ in the zone 18.
Adverse current logistics 18 ＇ have a region intermediate 19 ＇, and it is corresponding to the region intermediate 19 of tower 14.Similarly, adverse current logistics 18 ＇ have a bottom section 20 ＇ (corresponding to the bottom section 20 of tower 14), and a upper area 22 ＇ (corresponding to the upper area 22 of tower 14).And bottom section 20 ＇ of adverse current logistics 18 ＇ have a bottom 24 ＇ (corresponding to the bottom 24 of the bottom section 20 of tower 14).Upper area 22 ＇ of adverse current logistics 18 ＇ have a top 26 ＇ (corresponding to the top 26 of the upper area 22 of tower 14).
As in Fig. 1 as can be seen, adverse current logistics 18 ＇ are produced by second logistics (secondary streams) of a plurality of turnover towers 14.
One in these second logistics is the enriched material that enters region intermediate 19 ＇ of adverse current logistics 18 ＇.Another second logistics is the pimelinketone logistics, and the pimelinketone pipeline 30 at its bottom section 20 ＇ place by being positioned at adverse current logistics 18 ＇ is introduced.Another second logistics is the logistics of water, and the water pipeline 28 at its upper area 22 ＇ place by being positioned at adverse current logistics 18 ＇ is introduced.
Because the proportion of pimelinketone is littler than water, therefore it moves down (according to from bottom section 20 ＇ of the adverse current thing 18 ＇ direction to upper area 22 ＇) in tower 14, and water moves down (according to from upper area 22 ＇ of the adverse current logistics 18 ＇ direction to bottom section 20 ＇) in tower 14 simultaneously.Because two second logistics move with opposite direction, therefore the composition of adverse current logistics 18 ＇ changes with different places, finally cause near 24 ＇ of bottom forming and contain the water of the metal catalyst of major portion at least, and near 26 ＇ of top, form contain except that catalyzer, the pimelinketone phase of the enriched material of major portion at least.As extract and contain the water of major portion catalyzer, shift out by catalyst solution pipeline or extract pipeline 32, enriched material solution pipeline or raffinate pipeline 34 shifted out and pimelinketone communicates.
By this technology, realize the separation (dissolution) of enriched material, obtained by water extraction the metal catalyst of solution form simultaneously.Can be according to us described in above-mentioned patent of mentioning and the patent application, enriched material solution or raffinate and catalyst solution or extracting solution are further processed and/or circulate.
Can via catalyst solution pipeline or extract pipeline 32, extract and shift out whole basically metal catalysts by temperature and the material speed of control through pipeline 16,28 and 30.
The water that enters pipeline 28 can contain a spot of pimelinketone, and can contain a spot of water through the pimelinketone that pipeline 30 enters.Similarly, the catalyst solution in water or the extracting solution of discharging through pipeline 32 contain a small amount of pimelinketone, and the enriched material solution or the raffinate of discharging through pipeline 34 contain less water.
In the zone of the adverse current logistics with lower concentration catalyzer, top 22 ＇ of adverse current logistics 18 ＇ for example tend to contain the emulsification of the water and the pimelinketone of various products, and this makes little amount of catalyst be incorporated in enriched material solution or the raffinate pipeline 34.In order to reduce to a great extent or to eliminate this trend, the temperature of top 22 ＇ must be on a certain critical temperature, and this critical temperature can easily be found without too much experiment.Therefore, whole adverse current logistics 18 ＇ can remain on this critical temperature, perhaps 22 ＇ at an upper portion thereof at least only.The approach of the temperature of bottom 20 ＇ of a kind of simple control adverse current logistics 18 ＇, middle portion 19 ＇ and top 22 ＇ is, controls pimelinketone logistics through pipeline 30 respectively, through the enriched material logistics of pipeline 16 with through the temperature of the water logistics of pipeline 28.
Wishing that whole adverse current logistics remains under the situation of about uniform temp, preferred temperature range is 50～80 ℃.
Yet more preferably, the temperature of top 22 ＇ remains on 50～90 ℃ scope, and middle portion 19 ＇ remain on 30～50 ℃ scope, and bottom 20 ＇ remain on 10～40 ℃ scope.As mentioned above, a kind of mode of simple this purpose of realization is, control temperature respectively through the pimelinketone logistics of pipeline 30, temperature through the enriched material logistics of pipeline 16, with temperature through the water logistics of pipeline 28, yet this is optional, because be that realization this purpose can be used outside or inner heating or cooling, and/or the mode of other controlled temperature.
Refer now to Fig. 2, what its illustrated is a catalyst separating unit 110 that comprises vaporizer or distiller 112, and wherein vaporizer or distiller 112 are connected on the intermediate stage 119 of multistage counter-current extraction device 114 by line of pipes 116.Intermediate stage 119 comprises an intermediate separator 118 and a middle mixing tank 118a.Except that the intermediate stage 119, multistage counter-current extraction device also has an anterior stage 120 and the rear portion stage 122.There are an anterior separator 124 and an anterior mixing tank 124a in the anterior stage 120.Similarly, there are a rear portion separator 126 and a rear portion mixing tank 126a in the rear portion stage 122.Water pipeline 128 is connected on the mixing tank 126a of rear portion, and pimelinketone pipeline 130 is connected on the anterior mixing tank 124a.Extract pipeline 132 is connected on the anterior separator 124, and raffinate pipeline 134 is connected on the rear portion separator 126.
Also shown intermediate stage 136 and 138 among Fig. 2, they comprise intermediate separator 140 and 142 respectively, and middle mixing tank 140a and 142a.Yet according to situation separately and the degree of finishing extraction, the number in stage is the amount doesn't matter.
As the clear explanation of Fig. 2, each mixing tank and separator interconnect by the entrance and exit pipeline.Some source line combines mutually shown in the figure, forms the source line of single guiding mixing tank.Yet this is not essential.Source line can be separately and is directly guided mixing tank into.For the situation that has solid precipitation, this direct connection is particularly preferred.For simple and clear purpose, do not demonstrate among the figure in the pipeline various logistics are shifted to the pump of another container from a given container, and other annex, but they and they operate in is known in the art.
Separator can be decantor, centrifuge separator, or the separator that is suitable for being separated from each other two kinds of moving phases of other any kind.
Can heat different steps or the part in the stage (comprising mixing tank, separator, entrance and exit pipeline etc.) or cool off by any way well known in the art.For simplicity's sake, do not demonstrate heating/refrigerating unit among Fig. 1.
Vaporizer or distiller 112 are connected on the vapor line 115, and optional charge line 113 and the reaction mixture pipeline of handling 111 are connected on the vaporizer 112.Well heater or interchanger 117 are parts of vaporizer 112.
Before catalyzer extraction unit 110 or and afterwards device in Fig. 2, do not show because they were described in detail in the patent of our majority and application, here be incorporated herein by reference with application here.
In the operation of this embodiment, make from cyclohexane oxidation be the processing that comes of hexanodioic acid reaction mixture (as we patent and co-pending application described in, here they are incorporated herein by reference) enter into vaporizer or distiller 112 by pipeline 111.The mixture of handling is to remove remaining mixture behind the hexanodioic acid of major portion at least from reaction mixture, and above-mentioned reaction mixture is at acetate and metal catalyst, and preferred cobalt compound exists down, by being that hexanodioic acid makes with cyclohexane oxidation.The reaction mixture of handling can contain main or a spot of unreacted hexanaphthene.Can by reaction mixture is separated into (i) contain major portion acetate, hexanodioic acid, other polarity part and catalyzer polar phase and (ii) contain the nonpolar phase of the hexanaphthene of major portion, and remove hexanaphthene.Under such situation, recyclable nonpolar phase simultaneously can be by carrying out the hexanodioic acid that major portion is removed in crystallization from polar phase.Under this situation, after removing hexanodioic acid, residuum has constituted the reaction mixture of handling.Under another different situation, can remove hexanaphthene major portion or a spot of by the flash crystallization that carries out hexanodioic acid simultaneously.Under this situation, after removing hexanodioic acid, residuum has constituted the reaction mixture of handling.
Certainly, hexanaphthene can be removed by evaporation or any other technology.
Although it is in demand removing hexanaphthene before the reaction mixture of handling enters vaporizer or distiller 112, optional, recognize that this point is crucial.
The acetate of the major portion by evaporating existence is concentrated into a required degree with the reaction mixture that enters the processing of vaporizer 112.It is apparent that because its higher volatility, the hexanaphthene of any existence and most water will be by pipeline 115 evaporations, even before the acetate evaporation.It is highly important that, will leave away with the form of liquid by pipeline 116 by the enriched material that the acetate that evaporates major portion makes, even these liquid viscosity, but but still pumping.
In the process of evaporation of acetic acid, can add a spot of water continuously or off and on by charge line 113.Adding entry is important for the amount of acetate is minimized, and purpose is the factors such as relative quantity according to compound in transformation efficiency and the enriched material, and keeping enriched material is no solid form.
Enriched material enters intermediate stage 119 of multistage backflow device 114 through pipeline 116, and the logistics among logistics in the pipeline 116 and pipeline 140 ＇ merges, more backward with pipeline 142 " in logistics merge mixing tank 118a in the middle of ending at.From pipeline 116,140 ＇ and 142 " these three bursts of logistics thorough mixing in mixing tank 18a of coming, the gained mixture is delivered to separator 118 through pipeline 118a ＇, is separated into the top phase that is rich in pimelinketone in separator 118, with rich aqueous bottom mutually.The bottom is through pipeline 118 " deliver to the mixing tank (middle mixing tank 140a) of front, and the mixing tank (middle mixing tank 142a) of back is delivered on top through pipeline 118 ＇.
Pimelinketone is joined among the anterior mixing tank 124a through pipeline 130, there it with through pipeline 140 ", the logistics thorough mixing that comes mutually from middle separator 140 bottoms.The gained mixture joins in the anterior separator 124 through pipeline 124a ＇, and it is separated into through pipeline 132 bottom phase of discharging from device there, be sent to through pipeline 124 ＇ in the middle of mixing tank 140a top mutually.
Be the extract of the catalyzer of the major portion that contains aqueous solution form mutually from the bottom of installing discharging 114 through pipeline 132.It also contains a spot of pimelinketone.
In device rear portion stage 122 of 114, water enters mixing tank 126a through pipeline 128, there it with through pipeline 142 ＇, from the top of middle separator 142 mutually and the logistics thorough mixing.The gained mixture is sent to separator 126 through pipeline 126a ＇, there it be separated into the bottom mutually with top mutually.The bottom is through pipeline 126 " mixing tank 142a in the middle of being sent to, and top through pipeline 134 from installing discharging 114.
From installing the top phase of discharging 114, is the raffinate that contains the pimelinketone solution of major portion enriched material through pipeline 134.Wherein also there is a spot of water.
As shown in Figure 2, operation is based on stage of following several successive, promptly extract catalyzer and form final aqueous catalyst extract, through pipeline 132 from installing discharging 114, and stay enriched material raffinate in pimelinketone, this raffinate through pipeline 134 from installing discharging 114.
Because extraction solvent (water) shifts to anterior separator 124 from rear portion separator 126, so it is rich in catalyzer, stays the raffinate of removing catalyzer that increases continuously, this raffinate finally through pipeline 134 from installing discharging 114.
By this technology, realized entering the separation of the enriched material of multistage backflow device through pipeline 116, simultaneously by water extraction the metal catalyst of solution form.As described in our above-mentioned patent and the application, can be further processed and/or circulate raffinate and catalyzer extracting solution.
Introduce enriched material in intermediate stage of multistage backflow device or extractor (perhaps similarly the middle portion of counter-current tower), for from enriched material, extracting the efficient of catalyzer and the maximization of validity is very important.Intermediate stage 119 at multistage backflow device or extractor 114 is introduced enriched material, rather than introduces in the rear portion stage 122, has guaranteed that a considerable amount of catalyzer carry out being extracted before the last extraction at last separator 126.In the anterior stage 120 of multistage backflow device or extractor 114, introduce enriched material, will cause in the catalyzer extract of pipeline 132 dischargings, combining considerable enriched material part (non-catalytic).
Temperature by being controlled at different steps, through the feed rate of pipeline 128 and 130 and the number in stage, can extract and shift out whole basically metal catalysts through extracting solution pipeline 132.
The water that enters pipeline 128 can contain a small amount of pimelinketone, and can contain less water through the pimelinketone that pipeline 130 enters.Similarly, as mentioned above, contain a spot of pimelinketone through the catalyzer extracting solution of pipeline 132 dischargings, and contain a spot of water through the raffinate of pipeline 134 dischargings.
Close rear portion stage 122 of backflow device 114 by in the latter stage, should have quite low catalyst concn by latter stage, tend to contain the emulsification of the water and the pimelinketone of various products, this makes little amount of catalyst be incorporated in the raffinate of pipeline 134 discharging from device.In order to reduce to a great extent or to eliminate this trend, must be on a certain critical temperature by the temperature of latter stage, this critical temperature can easily be found without too much experiment.Therefore, all stages can remain on this critical temperature, perhaps only in leaning on latter stage, perhaps only in the rear portion stage 122.A kind of mode of simple this purpose of realization is, controls the temperature of each logistics in mode well known in the art, for example by well heater, water cooler and interchanger etc.Can certainly be by similar technology, separator or mixing tank are heated or cool off, for example use outside or inner heating or cooling and/or the mode of other controlled temperature.
Wishing that whole multistage backflow device remains under the situation of about uniform temp, preferred temperature range is 50～80 ℃.
Yet more preferably, the temperature in rear portion stage 122 should remain on 50～90 ℃ scope, and the temperature in middle part stage 119 should remain on 30～50 ℃ scope, and the temperature in anterior stage 120 should remain on 10～40 ℃ scope.In the presence of the intermediate stage, the temperature in intermediate stage preferably should remain between middle part phase temperature and each end stage (front portion or the rear portion) temperature.
If unacceptable emulsion occurs in rear portion stage 122 or what its stage in office, then as shown in Figure 1, available centrifuge separator such as separator 126 replace simple decantor.When using centrifuge separator at the rear portion in the stage at least, maintain the temperature on the emulsive stagnation point just so unimportant.
According to the present invention, should be understood that if in demand words, any liquid or gas or work off one's feeling vent one's spleen all can loop back any other parts from any part whole or in part.And can use the part or all of combination of any embodiment that exemplifies, or the arranging or combination of arranging of equal value of any equivalence, they are all within the scope of the present invention.
Although preferably control various functions by computer control unit, according to the present invention, can use the controller of any other type, perhaps manually control even and/or one or more functions of Artificial Control.Preferred computer control comprises artificial intelligence system (expert systems, neural network and fuzzy logic system, they are being known in the art).In this artificial intelligence system of three types, neural network is a learning system, it is from the different local acquisition of information (for example pressure, temperature, chemistry or other analysis etc.) of device, these information are stored together with result's (for example pressure reduction of speed rate, speed of reaction, reactivity etc.), and programming will be to use these information in future, and other operable data, make decision at situation about taking place under each situation.Expert systems is based on experienced expert opinion programming.Except that the special knowledge rule, fuzzy logic system is also based on the intuition rule.
According to oxidation of the present invention is nondestructive oxidation, wherein oxidation products be different from carbon monoxide, carbonic acid gas, and composition thereof, for example be hexanodioic acid.Certainly, a spot of these compounds can form together with oxidation products, and such oxidation products can be a kind of product or mixture of products.
As for hexanodioic acid, its preparation is particularly suitable for method of the present invention, except that other reference, can find the general information about it from many United States Patent (USP)s.These patents including but not limited to:
United States Patent (USP) 2223493; 2589648; 2285914; 3231608; 3234271; 3361806; 3390174; 3530185; 3649685; 3657334; 3957876; 3987100; 4032569; 4105856; 4158739 (pentanedioic acids); 4263453; 4331608; 4606863; 4902827; 5221800 and 5321157.
According to technology well known in the art, diprotic acid (for example hexanodioic acid, phthalic acid, m-phthalic acid and terephthalic acid etc.) or other suitable compounds, can with the 3rd reactant that is selected from polyvalent alcohol, polyamines and polynary acid amides, reaction forms polyester or polymeric amide or (polyimide and/or polyamidoimide) polymkeric substance respectively in some way.Excessively crosslinked for preventing, preferred polyol, polyamines and polynary acid amides are mainly dibasic alcohol, diamines and binary acid amides.The polymkeric substance that is obtained by this reaction can further be spun to fiber by technology well known in the art.This polymkeric substance can also mix with filler and/or other additive to form matrix material.
Provide the example of explanation the present invention operation, its purpose only is illustrative, is limitation of the present invention by any way and do not should be understood to.What should emphasize in addition is that the preferred embodiment of above-mentioned detailed description and any embodiment that other is included in the scope of the present invention can be implemented individually or in its any bonded mode according to general knowledge and/or expert opinion.According to the present invention, the unitary part of each embodiment also can be implemented separately, perhaps combines enforcement with other unitary part or its integral body of each embodiment.These combinations also within the scope of the invention.And the explanation of any trial only is a predictive in the specification sheets, and it is not to be meant to dwindle scope of the present invention.
Claims (21)
1. method of extracting metal catalyst from reaction mixture with the solution form, by being that hexanodioic acid makes with cyclohexane oxidation, this method comprises the steps: described reaction mixture in the presence of acetate and metal catalyst
(a) remove whole hexanaphthenes basically;
(b) remove the hexanodioic acid of major portion;
(c) not making the acetate of removing major portion under the catalyst precipitation, form the solution concentration thing thus;
(d) described enriched material is incorporated into the region intermediate of an adverse current logistics, this adverse current logistics also has a bottom section and a upper area, and bottom section has the bottom, and upper area has the top;
(e) pimelinketone that can contain less water is incorporated into the bottom section of described adverse current logistics;
(f) water that can contain a small amount of pimelinketone is incorporated into the upper area of described adverse current logistics;
(g) take out first liquid or raffinate from the top of upper area, this first liquid contains the enriched material of the major portion except that catalyzer; And
(h) take out second liquid or extract from the bottom of bottom section, this second liquid contains the metal catalyst of major portion.
2. the process of claim 1 wherein step (d), (e), (f), (g) and (h) carry out simultaneously.
3. each method of claim 1～2, wherein step (c) is undertaken by distillation.
4. each method of claim 1～3 further is included in the step that adds entry in the step (c).
5. each method of claim 1～4 is wherein removed whole basically acetate in step (c).
6. each method of claim 1～5 is wherein taken out whole basically metal catalysts in step (h).
7. each method of claim 1～6, there is a upper temp its middle and upper part, and middle portion has a middle portion temperature, and a bottom temperature is arranged at the bottom, and upper temp, middle portion temperature and temperature of lower are substantially the same.
8. each method of claim 1～6, there is a upper temp its middle and upper part, and middle portion has a middle portion temperature, and a bottom temperature is arranged at the bottom, and upper temp is higher than the temperature of middle portion.
9. the method for claim 8, wherein the temperature of middle portion is higher than temperature of lower.
10. each method of claim 1～9, further comprise in some way with hexanodioic acid and the step that is selected from a kind of reactant reaction of polyvalent alcohol, polyamine and polynary acid amides, to form polyester or polymeric amide or (polyimide and/or polyamidoimide) polymkeric substance respectively, this method can further comprise these polymkeric substance spinning are become fiber, or polymkeric substance is mixed with filler and/or other additive to form the step of matrix material.
11. a method of extracting metal catalyst from reaction mixture with the solution form, wherein said reaction mixture is in the presence of acetate and metal catalyst, and by what cyclohexane oxidation to hexanodioic acid was made, this method comprises the steps:
(k) remove whole hexanaphthenes basically;
(l) remove the hexanodioic acid of major portion;
(m) not making the acetate of removing major portion under the catalyst precipitation, form the solution concentration thing thus;
(n) described enriched material is incorporated into intermediate stage of an adverse current multistage device, this intermediate stage comprises a middle mixing zone and an intermediate section abscission zone, this adverse current multistage device also comprises an anterior stage and a rear portion stage, the anterior stage comprises an anterior mixing zone and a fore portion abscission zone, and the rear portion stage comprises mixing zone, a rear portion and abscission zone, a rear section;
(p) pimelinketone that can contain less water is incorporated into described anterior mixing zone;
(q) water that can contain a small amount of pimelinketone is incorporated into mixing zone, described rear portion;
(r) take out raffinate from the abscission zone, rear section, this raffinate contains the enriched material of the major portion except that catalyzer; And
(s) take out extract from the fore portion abscission zone, this extract contains the metal catalyst of major portion.
12. the method for claim 11, wherein step (m) is undertaken by distillation.
13. each method of claim 11～12 further is included in the step that adds entry in the step (m).
14. each method of claim 11～13 wherein at least in the abscission zone, rear section, is separated by centrifugation step at least in part.
15. each method of claim 11～14, there is a rear portion phase temperature in its postmedian stage, there is an intermediate stage temperature in intermediate stage, and there is an anterior phase temperature in the anterior stage, and rear portion phase temperature, intermediate stage temperature and anterior phase temperature are substantially the same.
16. the method for claim 15, wherein substantially the same temperature are in 50～80 ℃ scope.
17. each method of claim 1～14, there is a rear portion phase temperature in its postmedian stage, and there is an intermediate stage temperature in the intermediate stage, and there is an anterior phase temperature in the anterior stage, and the rear portion phase temperature is higher than the temperature in intermediate stage, and the temperature in intermediate stage is higher than the temperature in anterior stage.
18. the method for claim 17, the temperature range in its postmedian stage are 50～90 ℃, the temperature range in intermediate stage is 30～50 ℃, and the temperature range in anterior stage is 10～40 ℃.
19. each method of claim 1～18 is wherein removed whole basically acetate in step (m).
20. each method of claim 1～19 is wherein taken out whole basically metal catalysts in step (s).
21. the method for claim 11～20, further comprise in some way with hexanodioic acid and the step that is selected from a kind of reactant reaction of polyvalent alcohol, polyamine and polynary acid amides, to form polyester or polymeric amide or (polyimide and/or polyamidoimide) polymkeric substance respectively, this method can further comprise these polymkeric substance spinning are become fiber, or polymkeric substance is mixed with filler and/or other additive to form the step of matrix material.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12107099P | 1999-02-22 | 1999-02-22 | |
| US60/121,070 | 1999-02-22 | ||
| US12270599P | 1999-03-03 | 1999-03-03 | |
| US60/122,705 | 1999-03-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1344240A true CN1344240A (en) | 2002-04-10 |
Family
ID=26819052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00805435A Pending CN1344240A (en) | 1999-02-22 | 2000-02-14 | Methods of extracting catalyst in solution in mfg. adipic acid |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1154977A1 (en) |
| JP (1) | JP2002537279A (en) |
| KR (1) | KR20010105353A (en) |
| CN (1) | CN1344240A (en) |
| AU (1) | AU3372400A (en) |
| BR (1) | BR0008380A (en) |
| CA (1) | CA2363033A1 (en) |
| MX (1) | MXPA01008493A (en) |
| WO (1) | WO2000048981A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4916843B1 (en) * | 1970-03-24 | 1974-04-25 | ||
| FR2722783B1 (en) * | 1994-07-21 | 1996-08-30 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF ADIPIC ACID BY DIRECT OXIDATION OF CYCLOHEXANE AND RECYCLING OF THE CATALYST |
| DE4426132A1 (en) * | 1994-07-22 | 1996-01-25 | Bayer Ag | Dehydration of acetic acid in adipic acid mfr. without cobalt salt pptn. |
| DE4427474A1 (en) * | 1994-08-03 | 1996-02-08 | Bayer Ag | Adipic acid prepn. by oxidising cyclohexane with oxygen |
-
2000
- 2000-02-14 WO PCT/US2000/004473 patent/WO2000048981A1/en not_active Application Discontinuation
- 2000-02-14 CN CN00805435A patent/CN1344240A/en active Pending
- 2000-02-14 AU AU33724/00A patent/AU3372400A/en not_active Abandoned
- 2000-02-14 MX MXPA01008493A patent/MXPA01008493A/en unknown
- 2000-02-14 BR BR0008380-1A patent/BR0008380A/en not_active Application Discontinuation
- 2000-02-14 EP EP00911905A patent/EP1154977A1/en not_active Withdrawn
- 2000-02-14 JP JP2000599722A patent/JP2002537279A/en not_active Withdrawn
- 2000-02-14 KR KR1020017010654A patent/KR20010105353A/en not_active Application Discontinuation
- 2000-02-14 CA CA002363033A patent/CA2363033A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU3372400A (en) | 2000-09-04 |
| KR20010105353A (en) | 2001-11-28 |
| JP2002537279A (en) | 2002-11-05 |
| WO2000048981A1 (en) | 2000-08-24 |
| MXPA01008493A (en) | 2002-05-06 |
| CA2363033A1 (en) | 2000-08-24 |
| EP1154977A1 (en) | 2001-11-21 |
| BR0008380A (en) | 2002-02-19 |
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