CN101343210A - Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation - Google Patents
Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation Download PDFInfo
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- CN101343210A CN101343210A CNA2008100458438A CN200810045843A CN101343210A CN 101343210 A CN101343210 A CN 101343210A CN A2008100458438 A CNA2008100458438 A CN A2008100458438A CN 200810045843 A CN200810045843 A CN 200810045843A CN 101343210 A CN101343210 A CN 101343210A
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- phthalic anhydride
- bdo
- succinate
- acid
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- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000006227 byproduct Substances 0.000 title claims abstract description 43
- -1 succinic acid diester Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000001384 succinic acid Substances 0.000 title abstract description 7
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 title 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 63
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000047 product Substances 0.000 claims abstract description 46
- 239000002351 wastewater Substances 0.000 claims abstract description 40
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004821 distillation Methods 0.000 claims abstract description 27
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 22
- 230000032050 esterification Effects 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011976 maleic acid Substances 0.000 claims abstract description 21
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 239000001530 fumaric acid Substances 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 230000017105 transposition Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 8
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 238000010561 standard procedure Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 2
- 230000005945 translocation Effects 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 101100008044 Caenorhabditis elegans cut-1 gene Proteins 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 16
- 101100008046 Caenorhabditis elegans cut-2 gene Proteins 0.000 description 14
- 238000010992 reflux Methods 0.000 description 11
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for using by-products of phthalic anhydride to prepare BDO/succinic acid diester and phthalic acid diester, wherein, the by-products comprise at least one of wastewater, waste residues and phthalic anhydride residues, a preparation method thereof includes the major steps of esterification, distillation, reduction, etc., thereby obtaining a phthalic acid diester product, and also a BDO or succinic acid diester product. The method can fully recycle phthalic anhydride, phthalic acid, maleic anhydride, fumaric acid, maleic acid, succinic acid, etc. in the by-products such as wastewater, waste residues and phthalic anhydride residues in the production process of phthalic anhydride, thereby obtaining products such as chemical intermediate BDO or succinic acid diester and phthalic acid diester with great market demands, and maximally reducing the discharge of wastes; and the preparation method has advantages of simple and controllable technical process and rather low cost.
Description
Technical field
The invention belongs to chemical industry synthetic waste water and dregs processing technology field, particularly a kind of by product with phthalic anhydride production prepares the method for BDO/ succinate and Bisphthalate.
Background technology
The production method of phthalic anhydride mainly contains naphthalene oxidation style and o xylene oxidation method etc.In processes such as production, purification, equipment washing, can produce some acidic by-products, be called waste water after these acidic by-products are water-soluble, mainly contain Succinic Acid, butyric acid, acetate, toxilic acid, fumaric acid, phthalic acid and partial oxidation coupled product etc.; The solid of separating out automatically from the waste water that long-term (normally more than three months to several years) deposited is called waste residue, mainly contains phthalic acid, fumaric acid, also contains a spot of toxilic acid, Succinic Acid and high temperature oxidation, interlinkage, carbonization material etc.; In addition, also have a class by product to be meant that raw phthalic anhydride contains the lower material of phthalic anhydride concentration (being generally solid) through what back remnants were purified in distillation repeatedly, in present specification, be referred to as the phthalic anhydride slag, mainly contain phthalic anhydride, cis-butenedioic anhydride and high temperature oxidation, interlinkage, carbonization material etc.
In the prior art, all do not do recycling basically for waste water at present.For waste residue and phthalic anhydride slag, because preparation is comparatively difficult, do not do utilization basically yet, only there is a small amount of factory to utilize wherein cis-butenedioic anhydride or fumaric acid directly to use methanol esterification, crystallization obtains dimethyl fumarate then; Because the wherein influence of phthalic anhydride or phthalic acid, make that the methanol consumption amount is big, yield is low, and only recycled cis-butenedioic anhydride or fumaric acid wherein, economic benefit is not good.
Summary of the invention
The purpose of this invention is to provide a kind of by product and prepare BDO (1 with phthalic anhydride production, the 4-butyleneglycol)/method of succinate and Bisphthalate, not only can fully recycle phthalic anhydride in waste water, waste residue and the phthalic anhydride slag, phthalic acid, cis-butenedioic anhydride, fumaric acid, toxilic acid, Succinic Acid etc. by this method, also can obtain the great chemical intermediate BDO (1 of market demand, the 4-butyleneglycol)/succinate, and Bisphthalate, can make full use of the various by products in the phthalic anhydride production process, reduce discharging wastes to greatest extent.
The technical solution adopted for the present invention to solve the technical problems is:
Prepare the method for BDO/ succinate and Bisphthalate with the by product of phthalic anhydride production, described by product comprises at least a in waste water, waste residue, the phthalic anhydride slag, and its preparation method comprises following key step:
(1), esterification:
When only containing waste residue and/or phthalic anhydride slag in the by product, can directly carry out esterification;
When containing waste water in the by product, need earlier waste water to be concentrated or the transposition crystallization treatment, independent again or combine with other by product after carry out esterification;
Described esterification, be meant in above-mentioned by product or by product after treatment, add any one monohydroxy-alcohol be selected from C1-C8 (as can be) preferably from methyl alcohol, ethanol, propyl alcohol, butanols, octanol etc., in the presence of esterifying catalyst (can preferably in sulfuric acid, vitriol, solid super-strong acid, other Lewis acid etc. at least a), carry out sufficient esterification;
(2), distillation: after esterification is finished, adopt decompression or distillation under vacuum not, collecting boiling spread respectively is the overhead product 1 (containing succinate, maleic acid diester, dimethyl ester) of corresponding succinate, maleic acid diester, dimethyl ester mixture boiling spread and the overhead product 2 (being the Bisphthalate product) that boiling spread is the Bisphthalate boiling spread;
Adopt different distillating methods, perhaps adopt different alcohol to carry out esterification, collected overhead product 1 and overhead product 2 pairing boiling spreads are also different, as:
When adopting not distillation under vacuum, if adopt ethanol to carry out esterification, the boiling spread of collecting overhead product 1 is 190 ℃-240 ℃, and the boiling spread of collecting overhead product 2 is 285 ℃-305 ℃; If adopt methyl alcohol to carry out esterification, the boiling spread of collecting overhead product 1 is 170 ℃-230 ℃, and the boiling spread of collecting overhead product 2 is 270 ℃-290 ℃; Or the like;
And when adopting distillation under vacuum, then should be according to the boiling spread of the corresponding adjustment collection of vacuum tightness overhead product, make and contain succinate, maleic acid diester, dimethyl ester in the overhead product 1, containing Bisphthalate in the overhead product 2 (as: adopts propyl carbinol to carry out esterification, when vacuum tightness is 8mmHg, the boiling spread of collecting overhead product 1 is 110 ℃-170 ℃ (8mmHg), and the boiling spread of collecting overhead product 2 is 200 ℃-235 ℃ (8mmHg));
(3), reduction:
The overhead product 1 usefulness reduction maleic acid diester of above-mentioned distillation collection or the standard method of dimethyl ester are reduced, can obtain BDO or succinate product etc.
The standard method of reduction maleic acid diester or dimethyl ester can have multiple, as: adopt DAVY technology, reductive condition is: Cu series catalysts, 140-210 ℃, 40-80atm, H
2The time, reducible BDO, tetrahydrofuran (THF), the gamma-butyrolactone of obtaining, rectification and purification can obtain BDO, tetrahydrofuran (THF), gamma-butyrolactone product respectively again; And for example: adopt Zn/AcOH or hydrazine hydrate or Ni series catalysts to do selective reduction, maleic acid diester and dimethyl ester all can be converted into succinate, the rectifying purifying can obtain the succinate product.
In above-mentioned steps (1) esterification waste water concentrated or the method for transposition crystallization treatment, can be selected from any one of following three kinds of methods:
A, straight run distillation concentrate: distillation concentrates, and removes boiling point non-two acids low-molecular weight compound and water below 180 ℃, and enriched material is standby;
B, catalyzer transposition: partial concentration, after acid concentration (in toxilic acid, weight percent concentration) is 5%～70%, add the cis-trans position rotaring catalyst (as thiocarbamide, Sodium Bromide or other bromated compounds etc., add-on is the 0.1-10% of acid content (being the total mass of acid in the waste water)), at 50-110 ℃ of translocation reaction 2-24 hour, making the toxilic acid transposition was fumaric acid, cooling, crystallization, centrifugal, washing, drying, solid is standby;
C, heating transposition: partial concentration, after acid concentration (in toxilic acid, weight percent concentration) is 5%～70%, direct heating to 80 ℃～120 ℃, making the toxilic acid transposition is fumaric acid, cooling, crystallization, centrifugal, washing, drying, solid is standby.
Compared with prior art, the invention has the beneficial effects as follows:
Not only can fully recycle phthalic anhydride in the by products such as waste water, waste residue and phthalic anhydride slag in the phthalic anhydride production process, phthalic acid, cis-butenedioic anhydride, fumaric acid, toxilic acid, Succinic Acid etc. by the inventive method, also can obtain the great chemical intermediate BDO (1 of market demand, the 4-butyleneglycol)/succinate, and product such as Bisphthalate, can make full use of the various by products in the phthalic anhydride production process, reduce discharging wastes to greatest extent; And this preparation method's technological process simple controllable, cost is lower.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
Present embodiment is the method for preparing BDO and diethyl phthalate with the by product (waste water) that phthalic anhydride is produced, and concrete grammar is as follows:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, constantly replenish phthalic anhydride waste water in the process, to steam to remove enriched material behind most of water reach about 300 liters of volume, acid concentration surpass 70% (by toxilic acid, weight percent, down with) after, 120 ℃ of temperature in continuing to be warming up to, no longer include and stop heating when gas steams, remove vacuum;
In above-mentioned enriched material, add 650 liters of ethanol, the 20kg vitriol oil, reflux 8 hours, steam reclaim most of ethanol after, cooling transfers pH value to neutral with NaOH solution, continues distillation, collects 190-240 ℃ cut 1 and 285-305 ℃ cut 2; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is the diethyl phthalate product;
The cut 1 of above-mentioned collection is adopted the reduction of DAVY technology, and reductive condition is: the Cu series catalysts (BASF AG produces, model X-540, consumption be collected cut 1 weight 3%), 160-190 ℃, 50-70atm, H
2, reduction obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone, and rectification and purification promptly obtains the BDO product again, also obtains tetrahydrofuran (THF) and gamma-butyrolactone product simultaneously respectively.
Embodiment 2
Present embodiment is the method for preparing diethyl succinate and diethyl phthalate with the by product (waste water) that phthalic anhydride is produced, and concrete grammar is as follows:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, and constantly replenishes phthalic anhydride waste water in the process, extremely steaming reaches about 500 liters of volume, acid concentration above behind 50% (by the toxilic acid) except that the enriched material behind most of water, make up water to 1000 liter adds thiocarbamide 6kg, continues temperature rising reflux 3 hours, cooling, crystallization, centrifugal, the solid dry for standby;
Take by weighing solid 250kg, add 650 liters of ethanol, the 20kg vitriol oil with method for preparing, reflux 8 hours, steam reclaim most of ethanol after, cooling, transfer pH value to neutral with NaOH solution, continue distillation, collect 190-240 ℃ cut 1 and 285-305 ℃ cut 2; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is the diethyl phthalate product;
Cut 1 is directly adopted Zn/AcOH, and (the Zn consumption is 0.8 times of collected cut 1 weight, AcOH is 3 times of collected cut 1 weight) do selective reduction, maleic acid diester and dimethyl ester all are converted into diethyl succinate, and the rectifying purifying promptly obtains the diethyl succinate product.
Embodiment 3
Present embodiment is the method for preparing BDO and diethyl phthalate with the by product (waste water) that phthalic anhydride is produced, and concrete grammar is as follows:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, the additional phthalic anhydride waste water of section not in the process after steam removing enriched material behind most of water and reaching about 800 liters of volume, acid concentration and surpass 5% (by toxilic acid), continued temperature rising reflux 24 hours, cooling, crystallization, centrifugal, the solid dry for standby;
Take by weighing the solid 250kg that uses the one step process preparation, add 650 liters of ethanol, the 20kg vitriol oil, reflux 8 hours, steam reclaim most of ethanol after, cooling, transfer pH value to neutral with NaOH solution, continue distillation, collect 190-240 ℃ cut 1 and 285-305 ℃ cut 2; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is the diethyl phthalate product;
Cut 1 is adopted the reduction of DAVY technology, and reductive condition is: the Cu series catalysts (BASF AG produces, model X-540, collected cut 1 weight of consumption 2%), 140-160 ℃, 60-80atm, H
2, reduction obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone, and rectification and purification promptly obtains the BDO product again, also obtains tetrahydrofuran (THF) and gamma-butyrolactone product simultaneously respectively.
Embodiment 4
Present embodiment is the method for preparing diethyl succinate and diethyl phthalate with the by product (waste water, waste residue) that phthalic anhydride is produced, and concrete grammar is as follows:
Handle waste water according to following method:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, constantly replenish phthalic anhydride waste water in the process, extremely steaming reaches about 300 liters of volume, acid concentration above behind 50% (by the toxilic acid) except that the enriched material behind most of water, 80 ℃ of temperature in continuing to be warming up to, no longer include and stop heating when gas steams, remove vacuum;
Get prepared enriched material 130kg, other gets the by product waste residue 120kg that phthalic anhydride is produced, add 650 liters of ethanol, the 20kg vitriol oil, reflux 8 hours, steam reclaim most of ethanol after, cooling, transfer pH value to neutral with NaOH solution, continue distillation, collect 190-240 ℃ cut 1 and 285-305 ℃ cut 2; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is diethyl phthalate;
Adopt hydrazine hydrate (consumption is 0.8 times of collected cut 1 weight) to do selective reduction above-mentioned cut 1, ethyl maleate and DEF all are converted into diethyl succinate, the rectifying purifying promptly obtains the diethyl succinate product.
Embodiment 5
Present embodiment is the method for preparing BDO and dimethyl phthalate from the by product (waste water, phthalic anhydride slag) that phthalic anhydride is produced, and concrete grammar is as follows:
Handle waste water according to following method:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, and constantly replenishes phthalic anhydride waste water in the process, extremely steaming reaches about 600 liters of volume, acid concentration above behind 30% (by the toxilic acid) except that the enriched material behind most of water, make up water to 1000 liter adds Sodium Bromide 3kg, continues temperature rising reflux 24 hours, cooling, crystallization, centrifugal, the solid dry for standby;
Take the solid 130kg that aforesaid method makes, other gets the by product phthalic anhydride slag 120kg that phthalic anhydride is produced, add 650 liters of methyl alcohol, the 20kg vitriol oil, reflux 10 hours, steam reclaim most of methyl alcohol after, cooling, transfer pH value to neutral with NaOH solution, continue distillation, collect 170-230 ℃ cut 1 and 270-290 ℃ cut 2; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is dimethyl phthalate;
The cut 1 of above-mentioned collection is adopted the reduction of DAVY technology, and reductive condition is: the Cu series catalysts (BASF AG produces, model X-540, collected cut 1 weight of consumption 1%), 180-210 ℃, 40-60atm, H
2, reduction obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone, and rectification and purification promptly obtains the BDO product again, also obtains tetrahydrofuran (THF) and gamma-butyrolactone product simultaneously respectively.
Embodiment 6
Present embodiment is the method for preparing BDO and dibutyl phthalate with the by product (waste residue, phthalic anhydride slag) that phthalic anhydride is produced, and concrete grammar is as follows:
Get by product waste residue 120kg, phthalic anhydride slag 130kg that phthalic anhydride is produced, add 650 liters of propyl carbinols, the 20kg vitriol oil, reflux 10 hours, after steaming the most of propyl carbinol of recovery, cooling transfers pH value to neutrality with NaOH solution, the cut 1 of 110-170 ℃ (8mmHg) and the cut 2 of 200-235 ℃ (8mmHg) are collected in underpressure distillation; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is dibutyl phthalate;
The cut 1 of above-mentioned collection is adopted the reduction of DAVY technology, and reductive condition is: the Cu series catalysts (BASF AG produces, model X-540, consumption be collected cut 1 weight 5%), 160-180 ℃, 50-65atm, H
2, reduction obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone, and rectification and purification promptly obtains the BDO product again, also obtains tetrahydrofuran (THF) and gamma-butyrolactone product simultaneously respectively.
Embodiment 7
Present embodiment is the method for preparing dioctyl succinate and dioctyl phthalate (DOP) with the by product (waste water, waste residue, phthalic anhydride slag) that phthalic anhydride is produced, and concrete grammar is as follows:
Handle waste water according to following method:
In 1000 liters of reactors, add 900 liters of phthalic anhydride waste water, be decompressed to 40mmHg, distillation dewaters, the additional phthalic anhydride waste water of section not in the process after steam removing enriched material behind most of water and reaching about 800 liters of volume, acid concentration and surpass 15% (by toxilic acid), continued temperature rising reflux 24 hours, cooling, crystallization, centrifugal, the solid dry for standby;
Get the solid 130kg that makes, other gets waste residue 60kg, phthalic anhydride slag 60kg that phthalic anhydride is produced, adds 650 liters of n-Octanols, the 20kg vitriol oil, and reflux 10 hours dewaters with water trap in the reaction process; After having reacted, steam and reclaim most of n-Octanol, cooling transfers pH value to neutral with NaOH solution, and the cut 1 of 160-220 ℃ (8mmHg) and the cut 2 of 250-290 ℃ (8mmHg) are collected in underpressure distillation; Contain succinate, maleic acid diester, dimethyl ester in the cut 1, cut 2 is dioctyl phthalate (DOP);
Above-mentioned cut 1 is adopted Ni (consumption be collected cut weight 1%), H
2Do selective reduction, ethyl maleate and DEF all are converted into dioctyl succinate, the rectifying purifying promptly obtains the dioctyl succinate product.
Claims (7)
1. prepare the method for BDO/ succinate and Bisphthalate with the by product of phthalic anhydride production, it is characterized in that:
Described by product comprises at least a in waste water, waste residue, the phthalic anhydride slag, and its preparation method comprises following key step:
(1), esterification:
When only containing waste residue and/or phthalic anhydride slag in the by product, directly carry out esterification;
When containing waste water in the by product, earlier waste water is concentrated or the transposition crystallization treatment, independent again or combine with other by product after carry out esterification;
Described esterification is meant in above-mentioned by product or by product after treatment, adds any one monohydroxy-alcohol that is selected from C1-C8, in the presence of esterifying catalyst, carries out sufficient esterification;
(2), distillation: after esterification is finished, adopt decompression or distillation under vacuum not, collecting boiling spread respectively is the overhead product 1 of corresponding succinate, maleic acid diester, dimethyl ester mixture boiling spread and the overhead product 2 that boiling spread is the Bisphthalate boiling spread; Contain succinate, maleic acid diester, dimethyl ester in the overhead product 1; Overhead product 2 is the Bisphthalate product;
(3), reduction:
The overhead product 1 usefulness reduction maleic acid diester of above-mentioned distillation collection or the standard method of dimethyl ester are reduced, promptly obtain BDO or succinate product.
2. the by product with phthalic anhydride production according to claim 1 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
In described step (1) esterification, the monohydroxy-alcohol of C1-C8 is selected from any one in methyl alcohol, ethanol, propyl alcohol, butanols, the octanol.
3. the by product with phthalic anhydride production according to claim 1 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
In described step (1) esterification, esterifying catalyst is selected from least a in sulfuric acid, vitriol, solid super-strong acid, other Lewis acid.
4. the by product with phthalic anhydride production according to claim 1 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
In described step (1) esterification waste water concentrated or the method for transposition crystallization treatment, is selected from following three kinds of methods any one:
A, straight run distillation concentrate: boiling point non-two acids low-molecular weight compound and water below 180 ℃ are removed in distillation, and enriched material is standby;
B, catalyzer transposition: in toxilic acid, it is 5%～70% that waste water is concentrated into acid concentration, adds the cis-trans position rotaring catalyst, and its add-on is the 0.1-10% of sour total mass, at 50-110 ℃ of translocation reaction 2-24 hour, making the toxilic acid transposition is fumaric acid, cooling, crystallization, centrifugal, washing, drying, solid is standby;
C, heating transposition: in toxilic acid, it is 5%～70% that waste water is concentrated into acid concentration, direct heating to 80 ℃～120 ℃, and making the toxilic acid transposition is fumaric acid, cooling, crystallization, centrifugal, washing, drying, solid is standby.
5. the by product with phthalic anhydride production according to claim 4 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
Described cis-trans position rotaring catalyst is selected from thiocarbamide, Sodium Bromide, other bromated compounds.
6. the by product with phthalic anhydride production according to claim 1 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
DAVY technology is adopted in the standard method of described reduction maleic acid diester or dimethyl ester, and reductive condition is: Cu series catalysts, 140-210 ℃, 40-80atm, H
2, reduction obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone, and rectification and purification promptly obtains BDO, tetrahydrofuran (THF), gamma-butyrolactone product respectively again.
7. the by product with phthalic anhydride production according to claim 1 prepares the method for BDO/ succinate and Bisphthalate, it is characterized in that:
The standard method of described reduction maleic acid diester or dimethyl ester, adopt Zn/AcOH or hydrazine hydrate or Ni series catalysts to do selective reduction, maleic acid diester and dimethyl ester all are converted into succinate, and the rectifying purifying promptly obtains the succinate product.
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| CN2008100458438A CN101343210B (en) | 2008-08-21 | 2008-08-21 | Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation |
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| CN2008100458438A CN101343210B (en) | 2008-08-21 | 2008-08-21 | Method for preparing BDO/succinic acid diester and phthalandione diester with by-product from benzoic anhydride preparation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471218A (en) * | 2009-08-07 | 2012-05-23 | 因温斯特技术公司 | Hydrogenation and esterification to form diesters |
| CN103910635A (en) * | 2014-03-31 | 2014-07-09 | 辽宁正渤辽西环保产业园开发有限公司 | Recycling method for phthalic anhydride residues |
| CN105985532A (en) * | 2015-03-06 | 2016-10-05 | 镇江市凯普化学科技有限公司 | Method for producing compound plasticizer from fumaric acid production wastewater |
| GB2542447A (en) * | 2015-04-28 | 2017-03-22 | Johnson Matthey Davy Technologies Ltd | Process |
| CN106831429A (en) * | 2017-02-06 | 2017-06-13 | 常州工程职业技术学院 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
| CN112250569A (en) * | 2020-10-14 | 2021-01-22 | 云南大为恒远化工有限公司 | Method for preparing functional mixed plasticizer through pressure swing esterification |
| CN114538582A (en) * | 2022-01-29 | 2022-05-27 | 张志平 | Method and system for high-salt and high-COD sewage treatment and waste residue resource utilization |
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2008
- 2008-08-21 CN CN2008100458438A patent/CN101343210B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471218A (en) * | 2009-08-07 | 2012-05-23 | 因温斯特技术公司 | Hydrogenation and esterification to form diesters |
| CN102471218B (en) * | 2009-08-07 | 2014-11-05 | 因温斯特技术公司 | Hydrogenation and esterification to form diesters |
| CN103910635A (en) * | 2014-03-31 | 2014-07-09 | 辽宁正渤辽西环保产业园开发有限公司 | Recycling method for phthalic anhydride residues |
| CN105985532A (en) * | 2015-03-06 | 2016-10-05 | 镇江市凯普化学科技有限公司 | Method for producing compound plasticizer from fumaric acid production wastewater |
| GB2542447A (en) * | 2015-04-28 | 2017-03-22 | Johnson Matthey Davy Technologies Ltd | Process |
| GB2542447B (en) * | 2015-04-28 | 2017-09-13 | Johnson Matthey Davy Technologies Ltd | Process for recovering dialkyl succinate and/or dialkyl maleate |
| US10584091B2 (en) | 2015-04-28 | 2020-03-10 | Johnson Matthey Davy Technologies Limited | Process for the recovery of dialkyl succinate or dialkyl maleate |
| CN106831429A (en) * | 2017-02-06 | 2017-06-13 | 常州工程职业技术学院 | A kind of method that maleic anhydride waste residue prepares diethyl phthalate |
| CN112250569A (en) * | 2020-10-14 | 2021-01-22 | 云南大为恒远化工有限公司 | Method for preparing functional mixed plasticizer through pressure swing esterification |
| CN114538582A (en) * | 2022-01-29 | 2022-05-27 | 张志平 | Method and system for high-salt and high-COD sewage treatment and waste residue resource utilization |
| CN114538582B (en) * | 2022-01-29 | 2024-06-07 | 张志平 | Method and system for treating high-salt high-COD sewage and recycling waste residues |
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| CN101343210B (en) | 2011-03-30 |
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