CN110105303A - A method of using liquid chlorine as oxidant continuous production aniline fluid bed - Google Patents
A method of using liquid chlorine as oxidant continuous production aniline fluid bed Download PDFInfo
- Publication number
- CN110105303A CN110105303A CN201910543947.XA CN201910543947A CN110105303A CN 110105303 A CN110105303 A CN 110105303A CN 201910543947 A CN201910543947 A CN 201910543947A CN 110105303 A CN110105303 A CN 110105303A
- Authority
- CN
- China
- Prior art keywords
- mbt
- organic solvent
- accelerant
- cbs
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 87
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000007800 oxidant agent Substances 0.000 title claims abstract description 38
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 38
- 239000012530 fluid Substances 0.000 title claims abstract description 22
- 238000010924 continuous production Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 239000003960 organic solvent Substances 0.000 claims abstract description 61
- 238000009938 salting Methods 0.000 claims abstract description 57
- 239000000047 product Substances 0.000 claims abstract description 51
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 18
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 84
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000012043 crude product Substances 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 38
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 32
- 239000012071 phase Substances 0.000 claims description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000013019 agitation Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 10
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002242 deionisation method Methods 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000010348 incorporation Methods 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 20
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 19
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 19
- 239000002994 raw material Substances 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000460 chlorine Substances 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 139
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000013081 microcrystal Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- WILBJVMFOQPYOD-UHFFFAOYSA-N acetic acid propane-1,2,3-triol Chemical compound C(C)(=O)O.OCC(O)CO.OCC(O)CO.OCC(O)CO WILBJVMFOQPYOD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- KQPBSBAEBKRAAU-UHFFFAOYSA-N hypochlorous acid;sodium Chemical compound [Na].ClO KQPBSBAEBKRAAU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/76—Sulfur atoms attached to a second hetero atom
- C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, it the described method comprises the following steps: the salting liquid of accelerant MBT, ring amine, organic solvent, liquid chlorine being passed through in reactor and carry out oxidation reaction, CBS product is obtained after reaction product is post-treated；The reactor includes tubular reactor and/or micro passage reaction.The present invention can be using thick MBT as the direct synthesis accelerant CBS of raw material, and in-situ oxidation is carried out by oxidant of liquid chlorine, it can either avoid the problem that the consumption of caused raw material lye and chlorine is big in sodium hypochlorite production process, the waste water yield in CBS production process can be effectively controlled again, the overall efficiency of the method can be increased substantially, so that the method has industrialization promotion advantage.
Description
Technical field
The invention belongs to field of rubber technology, be related to a kind of method for producing aniline fluid bed, more particularly to it is a kind of with
Liquid chlorine is the method for oxidant continuous production aniline fluid bed.
Background technique
During with various rubber products such as rubber production tire, sebific duct and rubber overshoes, it is necessary to five big analog assistants are used,
They are thiofide, rubber antioxidant, the vulcanization of rubber and vulcanizing activator, processing type rubber chemicals and features
Property auxiliary agent.Wherein, thiofide abbreviation promotor is the substance for promoting sulfurization, can shorten vulcanization time, is reduced
Curing temperature reduces vulcanizing agent dosage and can be improved the physical mechanical property etc. of rubber.
Thiofide N cyclohexyl 2 benzothiazole sulfenamide (CBS) is the weight of sulfenamide type accelerators
One of kind is wanted, it is that a kind of common delayed vulcanization promoter, anticol burn function admirable, process safety, sulphur both at home and abroad
The change time is short, can improve the stretching strength and tensile strength of vulcanizate, is suitable for various rubber, discoloration is slight, no blooming.Rubber
Aniline fluid bed is mainly for the manufacture of industrial rubber articles such as tire, sebific duct, rubber overshoes and electric wires.
Currently, the industrialization method of rubber vulcanizing accelerator CBS is that will promote using sodium hypochlorite or hydrogen peroxide as oxidant
Agent 2- benzothiazolyl mercaptan (MBT) and ring amine oxidation generate accelerator CBS.Wherein, sodium hypochlorite oxidization has technique
Maturation, reaction condition is mild, product quality is preferable and the higher advantage of yield (generally in 90-92%), but applies hypochlorous acid
Sodium oxidizing process can generate a large amount of waste water, and salt content and COD higher in waste water when producing CBS, it is difficult to carry out biochemical treatment, no
Conducive to environmental protection.Peroxide passivation can overcome the problems, such as that salt content is high in waste water, but the activity of hydrogen peroxide is strong, in oxidation process
Side reaction also decreases compared with sodium hypochlorite oxidization sodium hypochlorite fado, product yield.Oxygen Catalytic Oxidation method is due to big
Amplitude reduction waste water yield, is conducive to environmental protection, but that there are conversion ratios is low for Oxygen Catalytic Oxidation method, and reaction speed is slow, work
The problems such as skill risk is high, and equipment investment is big affects the feasibility of its further industrialization conversion.
Currently, the CBS industrialized manufacturing technique of mainstream is based on autoclave intermittent reaction, no matter from throwing between batch and batch
There is certain fluctuation in the control in terms of the technological parameters such as doses, the temperature of reaction process and rate of feeding, and then to batch
Between the yield of product, quality exist it is more apparent influence, and then reduce the stability of industrialization production.Moreover, because mesh
Impurity content in preceding MBT is simultaneously unstable, and the composition in the MBT of different batches is inconsistent, further increases production promotor
The technology difficulty of CBS.
In addition, the CBS industrialized manufacturing technique of mainstream using commodity MBT as primary raw material, purity mostly 98% with
On, to obtain the MBT of such purity, industrially mostly use " acid-base method " or " solvent method " to thick MBT (i.e. after MBT high-pressure synthesis,
Not purified product) it is refined.Since " acid-base method " process for refining generates a large amount of intractable waste water, at present with gradually by
" solvent method " process for refining replaces.But it not only needs to be related to multiple high-risk process procedures in " solvent method " subtractive process, easily send out
Raw risk of explosion, simultaneously because MBT in solvent toluene there are certain solubility, can also lose at least 8% in subtractive process
Above MBT causes being significantly increased for wastage of material and cost.
Furthermore using sodium hypochlorite as the mainstream production technology of oxidant in the actual production process, can be related to hypochlorous acid
The problem of production of sodium, storage and transport, since sodium hypochlorite stability is poor, reducing atmosphere (storage medium be intolerant to
Easily belong to reducing atmosphere when corroding metal) or heated situation under be easy to decompose generate oxygen discharge simultaneously it is a large amount of hot, close
In border explosion accident easily occurs for closed loop, mostly by key monitoring in industrial processes.
106800540 A of CN discloses a kind of method for preparing rubber vulcanizing accelerator CBS using micro passage reaction,
This method dissolves MBT using excessive ring amine, and under the action of catalyst using hydrogen peroxide, sodium hypochlorite or oxygen, micro- logical
Synthesis accelerant CBS in road reactor.The micro passage reaction is made of micro-mixer and microchannel reactor two parts, wherein
Micro-mixer strengthens mixed effect with feature structure in pipeline, and microchannel reactor is the pipeline of internal diameter 1mm, single microchannel
The flux peak of reactor is only 15L/h, therefore the technical solution does not have capability of industrialization, and reaction yield is only 87-95%,
The purity of reaction product is equally unable to get guarantee.
106423033 A of CN and 106492719 A of CN discloses two kinds of microreactors, and the maximum of two kinds of microreactors is logical
Amount can achieve 1.8m3108570021 serialization disclosed in A and 108586295 A of CN of A, CN 108530383 of/h, CN
Continuous production is achieved the purpose that using microreactor in production method.Wherein, 108570021 A of CN discloses a kind of sulphur
Change accelerator CBS and its continuous production method, this method by the aqueous slkali of accelerant MBT, the acid solution of ring amine, solvent and
Oxidant, which is passed through in microreactor, carries out oxidation reaction, and reacting rear material obtains CBS product afterwards after post treatment.
But need to introduce a large amount of lye and acid solution, the system of raw material sodium hypochlorite in method disclosed in 108570021 A of CN
It is standby to also need to consume a large amount of lye and chlorine, so that generating a large amount of salinity, by-product chlorine during this method preparation CBS
The yield for changing sodium is about the 70% of CBS yield, and the business added value of sodium chloride is low, as can dropping in the technical process of production CBS
The generation of low sodium chloride, and guarantee the yield and purity of CBS simultaneously, for improving the profit of CBS product, improve the competition of enterprise
Power has great importance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide one kind using liquid chlorine as oxidant continuous production
The method of aniline fluid bed, when the method is overcome using commodity MBT as raw material, feedstock purification process losses are big, technique wind
The high problem in danger, while when to avoid sodium hypochlorite be oxidant, oxidant store that safety is poor, risk of explosion is high, and CBS is aoxidized
Synthesis process generates a large amount of waste water and low value-added sodium chloride, and the high problem of COD value in waste water；And the method also overcomes
When using hydrogen peroxide as oxidant, a large amount of byproducts are generated, the problem of making the purity of gained CBS reduces.
To achieve this purpose, the present invention adopts the following technical scheme:
The present invention provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method packet
Include following steps:
The salting liquid of accelerant MBT, ring amine, organic solvent, liquid chlorine are passed through in reactor and carry out oxidation reaction, is reacted
CBS product is obtained after product is post-treated.
The present invention is carried out with the salting liquid of accelerant MBT in the reactor by applying cyclohexylamine, organic solvent and liquid chlorine
Reaction, when the salting liquid for overcoming accelerant MBT is reacted with the acid solution of cyclohexylamine, generates a large amount of low value by-products
The problem of NaCl, while sodium hypochlorite storage when overcoming using sodium hypochlorite as oxidant, the security risk in transport are asked
Topic.
Oxidant used in the present invention is liquid chlorine, and liquid chlorine is different from sodium hypochlorite used in the process of conventional synthesis CBS and double
Oxygen water, (- 34.6 DEG C) of boiling point of liquid chlorine are far below temperature when oxidation reaction, when liquid chlorine, the salting liquid of accelerant MBT, hexamethylene
When amine and organic solvent are passed into reactor, liquid chlorine vaporization, thus carry out oxidation reaction in gas and water and oily three-phase,
The vaporization of liquid chlorine can not only provide oxidant chlorine, can reduce certain heat-transfer effect although vaporizing a large amount of bubbles of generation,
But the specific surface area of bubble is larger, with the reaction mass cooperation of turbulent flow operation in reactor, improves between reactant jointly
Contact effect, improve the utilization rate of reactant, moreover, oxidation reaction generate CBS product also can quickly be dissolved in
In organic solvent, the hypochlorous excessive contact for being dissolved in water generation with chlorine and chlorine is avoided, reduces and has generated product
Secondary oxidation further improves the yield of product.
The present invention is mixed in reactor using oil/water/gas phase reaction object, during strengthening mixing, without examining
The problem of considering side reaction.Therefore, the reaction time can be greatly reduced in the case where keeping product yield, so that the present invention is more
Has industrialization value.
Liquid chlorine oxidant used in the present invention is different from sodium hypochlorite and hydrogen peroxide disclosed in 108570021 A of CN, hypochlorous acid
The stability of sodium is poor, can be decomposed into oxygen and sodium chloride rapidly under oxidation reaction required temperature.Moreover, liquor natrii hypochloritis
Concentration it is not high, using liquor natrii hypochloritis as oxidant be applied to preparation CBS when, a large amount of high-salt wastewater can be generated；Dioxygen
Then there is secondary oxidation in water, be unfavorable for improving the purity of product；The application is that oxidant carries out situ oxygen using liquid chlorine
Change, both reduced in sodium hypochlorite production process as sodium hypochlorite decomposes and caused by raw material lye and chlorine consumption it is big
Problem, and can effectively control the waste water yield in CBS production process.
Preferably, the reactor includes tubular reactor and/or micro passage reaction, preferably C N106492719 A
And/or micro passage reaction disclosed in 106423033 A of CN.
The oxidation reaction of the application does not need addition catalyst, when being reacted in the reactor, connecing between reactant
Sufficiently, heat and mass transport is high-efficient, substantially reduces residence time of the reactant in flow reactor, can guarantee liquid chlorine for touching
Optimal reaction condition is kept in oxidation process in situ, and then salting liquid and ring that accelerant MBT is greatly improved are
The utilization rate of amine, improves yield.
Preferably, the accelerant MBT is commodity MBT and/or crude product MBT." commodity MBT " of the present invention is commercially available
Accelerant MBT, purity is higher, but the higher cost of purification process." crude product MBT " of the present invention is MBT high-pressure synthesis work
What sequence was expelled directly out, without the crude product MBT of any refinement treatment.
Thick MBT can be used as raw material in the present invention, and direct synthesis accelerant CBS, quotient must be used by overcoming traditional handicraft
Product MBT is as raw material, and then the problem of MBT must be purified.
The present invention configures the salting liquid of accelerant MBT in advance, then by the salting liquid of configured accelerant MBT, hexamethylene
Amine, organic solvent, liquid chlorine carry out the raw oxidation reaction of hybrid concurrency in micro passage reaction, overcome directly by accelerant MBT,
Cyclohexylamine and oxidant mixing bring accelerant MBT are contacted with oxidant, generate the risk of by-product MBTS.
Preferably, the preparation method of the salting liquid of the accelerant MBT is the following steps are included: accelerant MBT is being stirred
Under the conditions of mixed with organic solvent, aqueous slkali then is added under stirring, after MBT all dissolution after, stand split-phase, lower layer
Water phase is the salting liquid of accelerant MBT, and upper organic phase is organic solvent, as organic molten needed for oxidation reaction after separation
Agent, the isolated method are ordinary skill in the art means, and details are not described herein.
Preferably, the organic solvent includes methyl formate, methyl acetate, Ethyl formate, ethyl acetate, acetic acid triglycerin
In ester, chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene any one or at least two combination,
Typical but non-limiting combination includes the combination of methyl formate and methyl acetate, the combination of Ethyl formate and ethyl acetate, second
The combination of the combination of the combination of the combination of acetoacetic ester and toluene, chloroform and carbon tetrachloride, benzene and toluene, toluene and ethylbenzene,
The combination of benzene, toluene, ethylbenzene, isopropylbenzene and hexamethylene, the combination of methyl formate, methyl acetate, Ethyl formate and ethyl acetate
Or methyl formate, methyl acetate, Ethyl formate, ethyl acetate, acetic acid glyceryl ester, chloroform, carbon tetrachloride, benzene, toluene,
The combination of ethylbenzene, isopropylbenzene and hexamethylene, preferably ethyl acetate and/or toluene.
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2Any one in O or at least two
Combination, preferably NaOH solution, with the salting liquid of the accelerant MBT of NaOH solution preparation for M-Na salting liquid.
Preferably, the mass ratio of the accelerant MBT and organic solvent be 1:(1-10), such as can be 1:1,1:1.5,
1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:5、1:5.5、1:6、1:6.5、1:7、1:7.5、1:8、1:8.5、1:9、1:
9.5 or 1:10, preferably 1:(2.5-5).
Preferably, the accelerant MBT is under agitation 0-150 DEG C with the mixing temperature of organic solvent, such as can
Be 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C,
140 DEG C or 150 DEG C, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, excellent
It is selected as 0-40 DEG C.
Preferably, the accelerant MBT is under agitation 0.1-2h with the incorporation time of organic solvent, such as can be with
Be 0.1h, 0.2h, 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1.0h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h,
1.6h, 1.7h, 1.8h, 1.9h or 2.0h, it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
It is worth equally applicable, preferably 0.2-1h.
Preferably, the concentration of the aqueous slkali be 1-32wt%, such as can be 1wt%, 3wt%, 5wt%, 7wt%,
9wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt% or
32wt%, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 5-
20wt%.
Preferably, the mass ratio of the accelerant MBT and aqueous slkali be 1:(1.5-50), such as can be 1:1.5,1:2,
1:3、1:5、1:7、1:10、1:12、1:15、1:17、1:20、1:22、1:25、1:27、1:30、1:33、1:35、1:38、1:40、
1:42,1:44,1:46,1:48 or 1:50, it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
It is worth equally applicable, preferably 1:(2.5-9.6).
Preferably, the accelerant MBT is under agitation 0.1-2h with the incorporation time of aqueous slkali, such as be can be
0.1h、0.2h、0.3h、0.4h、0.5h、0.6h、0.7h、0.8h、0.9h、1h、1.1h、1.2h、1.3h、1.4h、1.5h、
1.6h, 1.7h, 1.8h, 1.9h or 2h, it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable, preferably 0.1-0.6h.
Preferably, the accelerant MBT is under agitation 0-100 DEG C with the mixing temperature of aqueous slkali, such as can be with
It is 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C, it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably 40-60 DEG C.
Preferably, it is described stand split-phase time of repose be 0.1-4h, such as can be 0.1h, 0.2h, 0.4h, 0.6h,
0.8h, 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.4h, 2.8h, 3.2h, 3.6h or 4h, it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable, preferably 0.5-2h.
Preferably, the charge-mass ratio of the salting liquid of the accelerant MBT and cyclohexylamine is 1:(0.01-1.5), such as can
To be 1:0.01,1:0.05,1:0.1,1:0.3,1:0.5,1:0.8,1:1,1:1.2,1:1.3,1:1.4 or 1:1.5, but not
It is only limitted to cited numerical value, other unlisted numerical value in the numberical range are equally applicable, preferably 1:(0.05-0.5).
Preferably, the charge-mass ratio of the salting liquid of the accelerant MBT and liquid chlorine is 1:(0.01-0.5), such as can be with
It is 1:0.01,1:0.05,1:0.1,1:0.15,1:0.25,1:0.35,1:0.4,1:0.45 or 1:0.5, it is not limited to institute
The numerical value enumerated, other unlisted numerical value in the numberical range are equally applicable, preferably 1:(0.04-0.15).
Preferably, the temperature of the oxidation reaction be 0-100 DEG C, such as can be 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C, 40 DEG C,
50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C, it is not limited to cited numerical value, in the numberical range other not
The numerical value enumerated is equally applicable, is preferably 20-50 DEG C.
Preferably, the time of the oxidation reaction be 0.5-240s, such as can be 0.5s, 1s, 2s, 3s, 4s, 5s, 6s,
7s, 8s, 9s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 100s, 120s, 140s, 160s, 180s, 200s, 220s or
240s, it is not limited to cited numerical value, other unlisted numerical value in the numberical range are equally applicable, preferably
0.5-10s。
Preferably, the post-processing is the following steps are included: reaction product obtains CBS and slightly produce after solvent recovery and filtering
Product obtain CBS product after CBS crude product is washed and dry.
Preferably, the solvent recovery is to be evaporated under reduced pressure to steam to solvent-free.
Preferably, the temperature of the solvent recovery is 20-80 DEG C, such as can be 20 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60
DEG C, 70 DEG C or 80 DEG C, it is not limited to cited numerical value, other unlisted numerical value in the numberical range are equally suitable
With preferably 40-50 DEG C.
Preferably, the vacuum degree of the solvent recovery be 1-80kPa, such as can be 1kPa, 5kPa, 10kPa, 15kPa,
20kPa, 25kPa, 30kPa, 35kPa, 40kPa, 45kPa, 50kPa, 55kPa, 60kPa, 65kPa, 70kPa, 75kPa or
80kPa, it is not limited to cited numerical value, other unlisted numerical value in the numberical range are equally applicable, preferably
1-50kPa。
Preferably, the washing is successively progress organic solvent washing and washing.
Preferably, the number of the organic solvent washing is 1-3 times, such as can be 1 time, 2 times or 3 times, preferably 1
It is secondary.
Preferably, when the organic solvent washing, organic solvent washing lotion and the liquid-solid ratio of accelerant MBT used in single are
(0.3-0.8): 1, such as can be 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1 or 0.8:1, it is not limited to cited
Numerical value, other unlisted numerical value in the numberical range are equally applicable, preferably 0.5:1.
Preferably, organic solvent washing lotion used includes methanol, ethyl alcohol, isopropanol, formic acid first when the organic solvent washing
It is any one in ester, methyl acetate, Ethyl formate, ethyl acetate, acetic acid glyceryl ester, acetone, tert-butylamine, cyclohexylamine or aniline
Kind aqueous solution or at least two combined aqueous solution, it is typical but non-limiting combination include methanol and ethanol composition water
Solution, the aqueous solution that methanol is combined with isopropanol, the aqueous solution that methyl formate is combined with methyl acetate, Ethyl formate and acetic acid second
The aqueous solution of ester combination, the aqueous solution that ethyl acetate is combined with acetic acid glyceryl ester, acetone, tert-butylamine, cyclohexylamine and aniline group
The aqueous solution of conjunction, the aqueous solution that methanol, ethyl alcohol are combined with isobutanol, methyl formate, methyl acetate, Ethyl formate, ethyl acetate
Combined aqueous solution or methanol, ethyl alcohol, isopropanol, methyl formate, methyl acetate, Ethyl formate, ethyl acetate, acetic acid triglycerin
The aqueous solution that ester, acetone, tert-butylamine, cyclohexylamine are combined with aniline, the preferably aqueous solution of cyclohexylamine.
Preferably, the number of the washing is 1-3 times, such as can be 1 time, 2 times or 3 times, preferably 2 times.
Preferably, the washing is to be washed using deionized water.
Preferably, when the washing, it is (0.3-0.8) that single, which washes deionized water used and the liquid-solid ratio of accelerant MBT:
1, such as can be 0.3:1,0.4:1,0.5:1,0.6:1,0.7:1 or 0.8:1, it is not limited to cited numerical value, it should
Other unlisted numerical value in numberical range are equally applicable, preferably 0.5:1.
As the optimal technical scheme of the method for the invention, described method includes following steps:
(1) under the conditions of 0-150 DEG C, by mass ratio be 1:(1-10) accelerant MBT and organic solvent in stirring condition
Then lower mixing 0.1-2h is added concentration under 0-100 DEG C, stirring condition and is the NaOH solution of 1-32wt%, and mixes 0.1-
The mass ratio of 2h, the accelerant MBT and NaOH solution is 1:(1.5-50), it stands 0.1-4h and carries out split-phase, lower layer's water phase is
For the salting liquid of accelerant MBT, upper organic phase is organic solvent, and upper organic phase is as organic solvent for aoxidizing after separation
Reaction；
(2) by the salting liquid of accelerant MBT, ring amine, MBT salting liquid configuring time division from obtained organic solvent, liquid
Chlorine is passed through in micro passage reaction, and oxidation reaction 0.5-240s is carried out at 0-100 DEG C, obtains reaction product, wherein promotor
The salting liquid of MBT and the charge-mass ratio of cyclohexylamine are 1:(0.01-1.5), the salting liquid of accelerant MBT and the charging matter of liquid chlorine
Amount is than being 1:(0.01-0.5)；
(3) recycling design is evaporated under reduced pressure under conditions of 20-80 DEG C and vacuum degree 1-80kPa in reaction product, using
It is obtained by filtration CBS crude product, successively the aqueous solution through cyclohexylamine washs 1-3 time, deionization washing 1-3 times and dry to CBS crude product
After dry, CBS product is obtained, wherein when the aqueous solution washing of cyclohexylamine, the aqueous solution and accelerant MBT of cyclohexylamine used in single
Liquid-solid ratio be (0.3-0.8): 1；When deionized water is washed, deionized water used in single and the liquid-solid ratio of accelerant MBT are
(0.3-0.8):1。
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
(1) present invention can eliminate the purification link of thick MBT, mention using thick MBT as the direct synthesis accelerant CBS of raw material
The utilization rate of active principle in high thick MBT, while avoiding the security risk of subtractive process；
(2) present invention is answered using the salting liquid of accelerant MBT, cyclohexylamine, organic solvent, liquid chlorine as raw material in microchannel plate
Aniline fluid bed is prepared in device, reaction speed is fast, product yield high, and with the content meter of accelerant MBT, yield is reachable
99.7%, by-product is few, and waste water COD is low；
(3) after cyclohexylamine is recycled in air-distillation, the COD in remaining water is reduced the waste water that the method for the invention obtains
To 2000ppm or less；
(4) present invention is that oxidant carries out in-situ oxidation using liquid chlorine, avoids the storage of sodium hypochlorite, in transportational process
Security risk, improve the safety coefficient of technique；
(5) present invention use liquid chlorine as oxidant, under alkaline condition oxidic raw materials acquisition product, avoid lye and
Hydrochloric acid reaction generates low value by-product sodium chloride, improves economic benefit；
(6) present invention carries out in-situ oxidation by oxidant of liquid chlorine, can either avoid causing in sodium hypochlorite production process
Raw material lye and chlorine the big problem of consumption, and can effectively control the waste water yield in CBS production process, Ke Yi great
Amplitude improves the overall efficiency of the method, so that the method has industrialization promotion advantage.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.But following specific embodiments are only
It is simple example of the invention, does not represent or limit the scope of the present invention, the scope of the present invention is wanted with right
It asks subject to book.
Specific embodiment of the invention part provides a kind of using liquid chlorine as oxidant continuous production aniline fluid bed
Method, described method includes following steps:
The salting liquid of accelerant MBT, cyclohexylamine, organic solvent, liquid chlorine are passed through in reactor and carry out oxidation reaction, is reacted
Product obtains CBS product afterwards after post treatment；
Wherein, the reactor includes tubular reactor and/or micro passage reaction.
The following are the typical but non-limiting embodiments of the present invention:
Embodiment 1
It present embodiments provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method
Include the following steps:
(1) under the conditions of 40 DEG C, the crude product MBT that mass ratio is 1:4.5 is mixed into 0.6h with toluene under agitation, so
The NaOH solution that concentration is 12wt% is added under 40 DEG C, stirring condition afterwards and continuess to mix 0.4h, the crude product MBT and NaOH
The mass ratio of solution is 1:5, stands split-phase after 1.5h, and lower layer's water phase is the salting liquid of accelerant MBT, and upper organic phase is to have
Solvent, upper organic phase is used for oxidation reaction as organic solvent after separation；
(2) the salting liquid configuring time division of the salting liquid of accelerant MBT, ring amine, accelerant MBT is organic molten from what is obtained
Agent and liquid chlorine are passed through in micro passage reaction, and oxidation reaction is carried out at 30 DEG C, and the residence time for controlling oxidation reaction is 4s,
Obtain reaction product, wherein the charge-mass ratio of the salting liquid of accelerant MBT and cyclohexylamine is 1:0.4, the salt of accelerant MBT
The charge-mass ratio of solution and liquid chlorine is 1:0.2, and the micro passage reaction is microchannel plate disclosed in 106492719 A of CN
Answer device, the salting liquid of accelerant MBT, cyclohexylamine, organic solvent and liquid chlorine total flow be 0.45m3/h；
(3) recycling design is evaporated under reduced pressure under conditions of 45 DEG C and vacuum degree 15kPa in reaction product, using filtering
To CBS crude product, CBS crude product successively after the aqueous solution of cyclohexylamine washing 1 time, deionization are washed 2 times and dried, is obtained
CBS product, wherein when the aqueous solution washing of cyclohexylamine, the aqueous solution of cyclohexylamine used and the liquid-solid ratio of accelerant MBT are 0.5:
1；When deionized water is washed, deionized water used in single and the liquid-solid ratio of accelerant MBT are 0.5:1.
Siccative weighing, the yield of CBS product are 99.7% (with the content meter of MBT in crude product MBT), the purity of CBS product
It is 99.7%, appearance is white micro-crystals powder, and the waste water generated in reaction process is remaining after normal pressure is distilled to recover organic solvent
COD is 1635ppm.
Embodiment 2
It present embodiments provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method
Include the following steps:
(1) under the conditions of 45 DEG C, the mixed solvent of crude product MBT and toluene/ethyl acetate that mass ratio is 1:4 are being stirred
Under the conditions of mix 1h, then under 45 DEG C, stirring condition be added concentration be 20wt% NaOH solution and continues to mix 0.2h, institute
The mass ratio for stating crude product MBT and NaOH solution is 1:3.8, stands split-phase after 1h, lower layer's water phase is that the salt of accelerant MBT is molten
Liquid, upper organic phase are organic solvent, and upper organic phase is used for oxidation reaction as organic solvent after separation；
(2) by the salting liquid of accelerant MBT, ring amine, accelerant MBT salting liquid configuring time division from obtained organic solution
And liquid chlorine is passed through in micro passage reaction, and oxidation reaction is carried out at 50 DEG C, the residence time for controlling oxidation reaction is 2s, is obtained
To reaction product, wherein the charge-mass ratio of the salting liquid of accelerant MBT and cyclohexylamine is 1:1.5, and the salt of accelerant MBT is molten
The charge-mass ratio of liquid and liquid chlorine is 1:0.35, and the micro passage reaction is that microchannel plate disclosed in 106492719 A of CN is answered
Device, the total flow of the salting liquid of accelerant MBT, the organic solution of cyclohexylamine and liquid chlorine are 0.9m3/h；
(3) recycling design is evaporated under reduced pressure under conditions of 50 DEG C and vacuum degree 25kPa in reaction product, using filtering
To CBS crude product, CBS crude product successively after the aqueous solution of ethyl alcohol washing 1 time, deionization are washed 2 times and dried, obtains CBS
Product, wherein when the aqueous solution washing of ethyl alcohol, the aqueous solution of ethyl alcohol used and the liquid-solid ratio of accelerant MBT are 0.6:1；Go from
When sub- water washing, the liquid-solid ratio of deionized water and accelerant MBT used in single is 0.6:1.
Siccative weighing, the yield of CBS product are 99.5% (with the content meter of MBT in crude product MBT), the purity of CBS product
It is 99.2%, appearance is white micro-crystals powder, and the waste water generated in reaction process is remaining after normal pressure is distilled to recover organic solvent
COD is 1740ppm.
Embodiment 3
It present embodiments provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method
Include the following steps:
(1) at 20 °C, the crude product MBT that mass ratio is 1:2.5 is mixed under agitation with ethyl acetate
0.8h, then under 20 DEG C, stirring condition be added concentration be 5wt% NaOH solution and continues to mix 1h, the crude product MBT with
The mass ratio of NaOH solution is 1:9.6, stands split-phase after 1h, lower layer's water phase is the salting liquid of accelerant MBT, upper organic phase
For organic solvent, upper organic phase is used for oxidation reaction as organic solvent after separation；
(2) the salting liquid configuring time division of the salting liquid of accelerant MBT, ring amine, accelerant MBT is organic molten from what is obtained
Agent and liquid chlorine are passed through in micro passage reaction, and oxidation reaction is carried out at 20 DEG C, and the residence time for controlling oxidation reaction is 5s,
Obtain reaction product, wherein the charge-mass ratio of the salting liquid of accelerant MBT and cyclohexylamine is 1:0.06, the salt of accelerant MBT
The charge-mass ratio of solution and liquid chlorine is 1:0.04, and the micro passage reaction is microchannel plate disclosed in 106492719 A of CN
Answer device, the salting liquid of accelerant MBT, cyclohexylamine, organic solvent and liquid chlorine total flow be 1.5m3/h；
(3) recycling design is evaporated under reduced pressure under conditions of 50 DEG C and vacuum degree 20kPa in reaction product, using filtering
To CBS crude product, CBS crude product successively after the aqueous solution of cyclohexylamine washing 1 time, deionization are washed 2 times and dried, is obtained
CBS product, wherein when the aqueous solution washing of cyclohexylamine, the aqueous solution of cyclohexylamine used and the liquid-solid ratio of accelerant MBT are 0.4:
1；When deionized water is washed, deionized water used in single and the liquid-solid ratio of accelerant MBT are 0.4:1.
Siccative weighing, the yield of CBS product are 99.7% (with the content meter of MBT in crude product MBT), the purity of CBS product
It is 99.3%, appearance is white micro-crystals powder, and the waste water generated in reaction process is remaining after normal pressure is distilled to recover organic solvent
COD is 1580ppm.
Embodiment 4
It present embodiments provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method
Include the following steps:
(1) under the conditions of 60 DEG C, the crude product MBT that mass ratio is 1:6 is mixed into 0.8h with cyclohexylamine under agitation, so
The NaOH solution that concentration is 32wt% is added under 60 DEG C, stirring condition afterwards and continuess to mix 2h, the crude product MBT and NaOH is molten
The mass ratio of liquid is 1:1.5, stands split-phase after 0.3h, and lower layer's water phase is the salting liquid of accelerant MBT, and upper organic phase is to have
Solvent, upper organic phase is used for oxidation reaction as organic solvent after separation；
(2) the salting liquid configuring time division of the salting liquid of accelerant MBT, ring amine, accelerant MBT is organic molten from what is obtained
Agent and liquid chlorine are passed through in micro passage reaction, and oxidation reaction is carried out at 60 DEG C, and the residence time for controlling oxidation reaction is
10s obtains reaction product, wherein the charge-mass ratio of the salting liquid of accelerant MBT and cyclohexylamine is 1:0.6, accelerant MBT
Salting liquid and the charge-mass ratio of liquid chlorine be 1:0.16, the micro passage reaction is micro- logical disclosed in 106492719 A of CN
Road reactor, the total flow of the salting liquid of accelerant MBT, the organic solution of cyclohexylamine and liquid chlorine are 0.18m3/h；
(4) recycling design is evaporated under reduced pressure under conditions of 60 DEG C and vacuum degree 15kPa in reaction product, using filtering
To CBS crude product, CBS crude product successively after the aqueous solution of aniline washing 1 time, deionization are washed 2 times and dried, obtains CBS
Product, wherein when the aqueous solution washing of aniline, the aqueous solution of aniline used and the liquid-solid ratio of accelerant MBT are 0.3:1；Go from
When sub- water washing, the liquid-solid ratio of deionized water and accelerant MBT used in single is 0.3:1.
Siccative weighing, the yield of CBS product are 92.5% (with the content meter of MBT in crude product MBT), the purity of CBS product
It is 99.3%, appearance is white micro-crystals powder, and the waste water generated in reaction process is remaining after normal pressure is distilled to recover organic solvent
COD is 1860ppm.
Embodiment 5
It present embodiments provides a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, the method
Include the following steps:
It (1) is that the crude product MBT of 1:6 and the mixing of hexamethylene/acetic acid glyceryl ester are molten by mass ratio under the conditions of 100 DEG C
Agent mixes 0.1h under agitation, and the NaOH solution that concentration is 1wt% and continuation are then added under 100 DEG C, stirring condition
Mixing 0.4h, the crude product MBT and the mass ratio of NaOH solution are 1:50, stand split-phase after 4h, lower layer's water phase is the salt of MBT
Solution, upper organic phase are organic solvent, are used for oxidation reaction as organic solvent after separation；
(2) by the salting liquid of accelerant MBT, ring amine, configure the salting liquid of accelerant MBT when it is isolated organic molten
Agent and liquid chlorine are passed through in micro passage reaction, and oxidation reaction is carried out at 100 DEG C, and the residence time for controlling oxidation reaction is
240s obtains reaction product, wherein the charge-mass ratio of the salting liquid of accelerant MBT and cyclohexylamine is 1:0.03, promotor
The salting liquid of MBT and the charge-mass ratio of liquid chlorine are 1:0.01, and the micro passage reaction is disclosed in 106492719 A of CN
Micro passage reaction, the total flow of the salting liquid of accelerant MBT, the organic solution of cyclohexylamine and liquid chlorine are 1.8m3/h；
(3) recycling design is evaporated under reduced pressure under conditions of 50 DEG C and vacuum degree 10kPa in reaction product, using filtering
To CBS crude product, CBS crude product successively after the aqueous solution of aniline washing 1 time, deionization are washed 2 times and dried, obtains CBS
Product, wherein when the aqueous solution washing of aniline, the aqueous solution of aniline used and the liquid-solid ratio of accelerant MBT are 0.8:1；Go from
When sub- water washing, the liquid-solid ratio of deionized water and accelerant MBT used in single is 0.8:1.
Siccative weighing, the yield of CBS product are 88.5% (with the content meter of MBT in crude product MBT), the purity of CBS product
It is 99.1%, appearance is white micro-crystals powder, and the waste water generated in reaction process is remaining after normal pressure is distilled to recover organic solvent
COD is 1750ppm.
Embodiment 6
Present embodiments provide it is a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, except by step
(1) outside the commercially available MBT of MBT amount such as the crude product MBT in is replaced with, remaining is same as Example 1.
Although commercially available MBT purity is higher, significant difference, product are had no when the product yield of CBS is with using crude product MBT
Appearance is white micro-crystals powder, and after measured, the product yield of CBS is 99.7% (with the content meter of MBT in commercially available MBT), and CBS is produced
The purity of product is 99.7%, and for waste water after normal pressure is distilled to recover organic solvent, remaining COD is 1585ppm.
Embodiment 7
Present embodiments provide it is a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, remove step (3)
The salting liquid of middle accelerant MBT and the charge-mass ratio of liquid chlorine are outside 1:0.6, remaining is same as Example 1.
Since the additive amount of oxidant is more, secondary oxidation easily occurs for gained CBS product, and the purity of CBS is caused to reduce, and
And the time of oxidation reaction of the present invention is short, excessive oxidant can generate excessive chlorine, environmental pollution be caused, although producing
Product appearance is white micro-crystals powder, but by measurement, the product yield of CBS is 77.6% (with the content of MBT in crude product MBT
Meter), the purity of CBS product is 97.6%, and for waste water after normal pressure is distilled to recover organic solvent, remaining COD is 6850ppm.
Embodiment 8
Present embodiments provide it is a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, remove step (3)
The salting liquid of middle accelerant MBT and the charge-mass ratio of liquid chlorine are outside 1:0.008, remaining is same as Example 1.
Since the additive amount of oxidant is less, oxidation reaction almost without, by measurement, final gained CBS product
Yield is only 7.8% (with the content meter of MBT in crude product MBT), and the purity of CBS product is only 8.5%, and waste water is returned through air-distillation
After receiving organic solvent, remaining COD is 68750ppm.
Comparative example 1
This comparative example provides a kind of aniline fluid bed a kind of as disclosed in the embodiment 1 of 108570021 A of CN
Continuous production method.
After measured, the CBS yield that 1 providing method of comparative example is prepared is 99.6% (with the content meter of accelerant MBT),
The purity of CBS is 99.6wt%, and appearance is white micro-crystals powder, and after normal pressure is distilled to recover cyclohexylamine, remaining COD is waste water
1900ppm。
Comparative example 2
This comparative example provides a kind of aniline fluid bed a kind of as disclosed in the embodiment 3 of 108570021 A of CN
Continuous production method.
After measured, the CBS yield that 2 providing method of comparative example is prepared is 95.3% (with the content meter of accelerant MBT),
The purity of CBS is 98.9wt%, and appearance is white micro-crystals powder, and after normal pressure is distilled to recover cyclohexylamine, remaining COD is waste water
1950ppm。
In conclusion the present invention can improve in thick MBT effective group using thick MBT as the direct synthesis accelerant CBS of raw material
The utilization rate divided；And the present invention is using the salting liquid of accelerant MBT, cyclohexylamine, organic solvent, liquid chlorine as raw material, in microchannel
Aniline fluid bed is prepared in reactor, reaction speed is fast, product yield high, and with the content meter of accelerant MBT, yield is reachable
99.7%；The present invention carries out in-situ oxidation by oxidant of liquid chlorine, can either avoid caused original in sodium hypochlorite production process
Expect the big problem of the consumption of lye and chlorine, and can effectively control the waste water yield in CBS production process, passes through waste water
After cyclohexylamine is recycled in air-distillation, the COD in remaining water is reduced to 2000ppm hereinafter, the present invention increases substantially the method
Overall efficiency so that the method have industrialization promotion advantage.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of using liquid chlorine as the method for oxidant continuous production aniline fluid bed, which is characterized in that the method includes with
Lower step:
The salting liquid of accelerant MBT, ring amine, organic solvent and liquid chlorine are passed through in reactor and carry out oxidation reaction, is reacted
CBS product is obtained after product is post-treated.
2. the method according to claim 1, wherein the reactor includes tubular reactor and/or microchannel
Reactor.
3. method according to claim 1 or 2, which is characterized in that the preparation method packet of the salting liquid of the accelerant MBT
It includes following steps: accelerant MBT being mixed with organic solvent under agitation, aqueous slkali then is added under stirring,
After accelerant MBT all dissolution, split-phase is stood, lower layer's water phase is the salting liquid of accelerant MBT, and upper organic phase is organic
Solvent, as organic solvent needed for the oxidation reaction after separation；
Preferably, the organic solvent include methyl formate, methyl acetate, Ethyl formate, ethyl acetate, acetic acid glyceryl ester,
In chloroform, carbon tetrachloride, benzene, toluene, ethylbenzene, isopropylbenzene or hexamethylene any one or at least two combination, it is excellent
It is selected as ethyl acetate and/or toluene；
Preferably, the aqueous slkali includes NaOH solution, KOH solution or NH3·H2In O any one or at least two group
It closes, preferably NaOH solution.
4. method according to claim 1-3, which is characterized in that the accelerant MBT be commodity MBT and/or
Crude product MBT；
The crude product MBT is what MBT high-pressure synthesis process was expelled directly out, without the crude product MBT of any refinement treatment.
5. according to the method described in claim 3, it is characterized in that, the mass ratio of the accelerant MBT and organic solvent is 1:
(1-10), preferably 1:(2.5-5)；
Preferably, the accelerant MBT under agitation with the mixing temperature of organic solvent be 0-150 DEG C, preferably 0-
40℃；
Preferably, the accelerant MBT is under agitation 0.1-2h, preferably 0.2- with the incorporation time of organic solvent
1h。
6. according to the method described in claim 3, it is characterized in that, the concentration of the aqueous slkali is 1-32wt%, preferably 5-
20wt%；
Preferably, the mass ratio of the accelerant MBT and aqueous slkali is 1:(1.5-50), preferably 1:(2.5-9.6)；
Preferably, the accelerant MBT is under agitation 0.1-2h, preferably 0.1- with the incorporation time of aqueous slkali
0.6h；
Preferably, the accelerant MBT is under agitation 0-100 DEG C with the mixing temperature of aqueous slkali, preferably 40-60
℃；
Preferably, the time of repose for standing split-phase is 0.1-4h, preferably 0.5-2h.
7. method according to claim 1-6, which is characterized in that the salting liquid and hexamethylene of the accelerant MBT
The charge-mass ratio of amine is 1:(0.01-1.5), preferably 1:(0.05-0.5)；
Preferably, the charge-mass ratio of the salting liquid of the accelerant MBT and liquid chlorine is 1:(0.01-0.5), preferably 1:
(0.04-0.15)；
Preferably, the temperature of the oxidation reaction is 0-100 DEG C, is preferably 20-50 DEG C；
Preferably, the time of the oxidation reaction is 0.5-240s, preferably 0.5-10s.
8. method according to claim 1-7, which is characterized in that the post-processing is the following steps are included: reaction
Product obtains CBS crude product after solvent recovery and filtering, obtains CBS product after CBS crude product is washed and dry.
9. according to the method described in claim 8, it is characterized in that, the solvent recovery is to be evaporated under reduced pressure to steam to solvent-free；
Preferably, the temperature of the solvent recovery is 20-80 DEG C, preferably 40-50 DEG C；
Preferably, the vacuum degree of the solvent recovery is 1-80kPa, preferably 1-50kPa；
Preferably, the washing is successively progress organic solvent washing and washing；
Preferably, the number of the organic solvent washing is 1-3 times, preferably 1 time；
Preferably, when the organic solvent washing, organic solvent washing lotion and the liquid-solid ratio of accelerant MBT used in single are (0.3-
0.8): 1, preferably 0.5:1；
Preferably, organic solvent washing lotion used includes methanol, ethyl alcohol, isopropanol, methyl formate, second when the organic solvent washing
In sour methyl esters, Ethyl formate, ethyl acetate, acetic acid glyceryl ester, acetone, tert-butylamine, cyclohexylamine or aniline any one
Aqueous solution or at least two combined aqueous solution, the preferably aqueous solution of cyclohexylamine；
Preferably, the number of the washing is 1-3 times, preferably 2 times；
Preferably, the washing is to be washed using deionized water；
Preferably, when the washing, it is (0.3-0.8) that single, which washes deionized water used and the liquid-solid ratio of accelerant MBT: 1, it is excellent
It is selected as 0.5:1.
10. -9 described in any item methods according to claim 1, which is characterized in that described method includes following steps:
(1) under the conditions of 0-150 DEG C, the accelerant MBT by mass ratio for 1:(1-10) mixes under agitation with organic solvent
Close 0.1-2h, then 0-100 DEG C, the NaOH solution that concentration is 1-32wt% is added under agitation, and mix 0.1-2h,
The accelerant MBT and the mass ratio of NaOH solution are 1:(1.5-50), it stands 0.1-4h and carries out split-phase, lower layer's water phase is to promote
Into the salting liquid of agent MBT, upper organic phase is organic solvent, and upper organic phase is anti-for aoxidizing as organic solvent after separation
It answers；
(2) the salting liquid configuring time division of the salting liquid of accelerant MBT, ring amine, MBT are led to from obtained organic solvent, liquid chlorine
Enter in micro passage reaction, oxidation reaction 0.5-240s is carried out at 0-100 DEG C, obtains reaction product, wherein accelerant MBT
Salting liquid and cyclohexylamine charge-mass ratio be 1:(0.01-1.5), the salting liquid of accelerant MBT and the feedstock quality of liquid chlorine
Than for 1:(0.01-0.5)；
(3) recycling design is evaporated under reduced pressure under conditions of 20-80 DEG C and vacuum degree 1-80kPa in reaction product, using filtering
Obtain CBS crude product, CBS crude product successively after the aqueous solution of cyclohexylamine washs 1-3 time, deionization washes 1-3 times and dry,
Obtain CBS product, wherein when the aqueous solution washing of cyclohexylamine, the aqueous solution of cyclohexylamine used in single and the liquid of accelerant MBT are solid
Than for (0.3-0.8): 1；When deionized water is washed, deionized water used in single and the liquid-solid ratio of accelerant MBT are (0.3-
0.8):1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910543947.XA CN110105303A (en) | 2019-06-21 | 2019-06-21 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910543947.XA CN110105303A (en) | 2019-06-21 | 2019-06-21 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110105303A true CN110105303A (en) | 2019-08-09 |
Family
ID=67495741
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910543947.XA Pending CN110105303A (en) | 2019-06-21 | 2019-06-21 | A method of using liquid chlorine as oxidant continuous production aniline fluid bed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110105303A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024484A (en) * | 2019-12-25 | 2021-06-25 | 北京彤程创展科技有限公司 | Method for purifying and preparing high-purity promoter CZ and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1940364A1 (en) * | 1969-08-08 | 1971-02-18 | Bayer Ag | Process for the preparation of Benzthiazylsulfenamiden |
| CN102863402A (en) * | 2012-09-25 | 2013-01-09 | 科迈化工股份有限公司 | Preparation method of accelerator CBS |
| CN104592161A (en) * | 2014-12-29 | 2015-05-06 | 内蒙古科迈化工有限公司 | Method for producing rubber vulcanization accelerator CBS by crude product MBT |
| CN105541755A (en) * | 2015-12-17 | 2016-05-04 | 科迈化工股份有限公司 | Synthetic method for rubber vulcanizing accelerator CZ with sodium hypochlorite as oxidizing agent |
| CN106423033A (en) * | 2016-10-31 | 2017-02-22 | 山东豪迈化工技术有限公司 | Micro-reactor |
| CN106492719A (en) * | 2016-10-31 | 2017-03-15 | 山东豪迈化工技术有限公司 | A kind of microreactor |
| CN106699684A (en) * | 2016-12-21 | 2017-05-24 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
| CN108530383A (en) * | 2018-05-23 | 2018-09-14 | 科迈化工股份有限公司 | A kind of vulcanization accelerator TBBS and its continuous production method |
| CN108570021A (en) * | 2018-05-23 | 2018-09-25 | 科迈化工股份有限公司 | A kind of aniline fluid bed and its continuous production method |
| CN108586295A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D PG |
-
2019
- 2019-06-21 CN CN201910543947.XA patent/CN110105303A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1940364A1 (en) * | 1969-08-08 | 1971-02-18 | Bayer Ag | Process for the preparation of Benzthiazylsulfenamiden |
| FR2056748A5 (en) * | 1969-08-08 | 1971-05-14 | Bayer Ag | Benzothiazyl sulphenamides prepn |
| CN102863402A (en) * | 2012-09-25 | 2013-01-09 | 科迈化工股份有限公司 | Preparation method of accelerator CBS |
| CN104592161A (en) * | 2014-12-29 | 2015-05-06 | 内蒙古科迈化工有限公司 | Method for producing rubber vulcanization accelerator CBS by crude product MBT |
| CN105541755A (en) * | 2015-12-17 | 2016-05-04 | 科迈化工股份有限公司 | Synthetic method for rubber vulcanizing accelerator CZ with sodium hypochlorite as oxidizing agent |
| CN106423033A (en) * | 2016-10-31 | 2017-02-22 | 山东豪迈化工技术有限公司 | Micro-reactor |
| CN106492719A (en) * | 2016-10-31 | 2017-03-15 | 山东豪迈化工技术有限公司 | A kind of microreactor |
| CN106699684A (en) * | 2016-12-21 | 2017-05-24 | 科迈化工股份有限公司 | Method for producing rubber vulcanization accelerator CZ |
| CN106800540A (en) * | 2017-03-30 | 2017-06-06 | 山东斯递尔化工科技有限公司 | A kind of method that utilization micro passage reaction prepares rubber vulcanizing accelerator CBS |
| CN108530383A (en) * | 2018-05-23 | 2018-09-14 | 科迈化工股份有限公司 | A kind of vulcanization accelerator TBBS and its continuous production method |
| CN108570021A (en) * | 2018-05-23 | 2018-09-25 | 科迈化工股份有限公司 | A kind of aniline fluid bed and its continuous production method |
| CN108586295A (en) * | 2018-05-23 | 2018-09-28 | 科迈化工股份有限公司 | A kind of continuous production method of accelerator D PG |
Non-Patent Citations (3)
| Title |
|---|
| SHANYU TANG等: "Scalable electrochemical oxidant-and metal-free dehydrogenative coupling of S-H/N-H", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
| 孟庆森: "促进剂CBBS合成工艺研究", 《橡胶科技》 * |
| 孟庆森等: "以微通道反应器为基础生产促进剂CBS的产业化研究", 《橡塑领域化工产业化示范工程大会》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113024484A (en) * | 2019-12-25 | 2021-06-25 | 北京彤程创展科技有限公司 | Method for purifying and preparing high-purity promoter CZ and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110156718A (en) | A method of using liquid chlorine as oxidant continuous production accelerator D CBS | |
| CN104628548B (en) | Method for preparing acetophenone by bionic catalytic oxidation of ethylbenzene | |
| CN108586383A (en) | A kind of continuous production method of accelerator D CBS | |
| CN108530383A (en) | A kind of vulcanization accelerator TBBS and its continuous production method | |
| CN108570021B (en) | Vulcanization accelerator CBS and continuous production method thereof | |
| CN113956135B (en) | Preparation method of high-yield 4,4' -biphenol | |
| CN108586295A (en) | A kind of continuous production method of accelerator D PG | |
| CN101613330A (en) | The method of preparing cyclohexene oxide through hydrogen peroxide epoxidation | |
| CN110105303A (en) | A method of using liquid chlorine as oxidant continuous production aniline fluid bed | |
| CN108191675A (en) | The method that paraphenetidine is prepared with the device catalytic hydrogenation of industrially scalable | |
| CN107082892A (en) | A kind of preparation method of bimetallic organic framework material and its application in cyclohexylhydroperoxdecomposition decomposition reaction | |
| CN104447672A (en) | Method for synthesizing epsilon-caprolactone by using active carbon immobilized heteropoly acid | |
| CN101092428B (en) | New technique for preparing glyphosate by oxidizing N-Phosphonomethyl iminodiacetic acid in air | |
| CN115160127B (en) | Method for preparing long carbon chain dibasic acid through co-oxidation reaction | |
| CN110903181B (en) | Method for preparing p-benzoquinone compound by double-catalytic system | |
| CN107513047B (en) | Green process for synthesizing ceftazidime side chain acid active ester by microwave-assisted method | |
| CN107445959B (en) | A kind of preparation method of 2- azabicyclo [2.2.1]-hept- 5- alkene -3- ketone | |
| CN110105304A (en) | A method of using liquid chlorine as oxidant continuous production vulcanization accelerator TBBS | |
| CN103420777A (en) | Method for continuously synthesizing 1, 5, 9-cyclododecatriene | |
| CN102993131A (en) | Method for preparing cyclohexene oxide by cyclization of o-chlorocyclohexanol | |
| CN1562470A (en) | Nickel base catalyst of burst cooling framework in use for preparing hydrogen peroxide by adding hydrogen to 2-ethyl-anthraquinone | |
| CN103923056A (en) | Synthetic method of 3, 4-methylene dioxybenzaldehyde | |
| CN101381323B (en) | Method for preparing p-aminobenzoic acid from p-nitrobenzoic acid | |
| CN101092343B (en) | Method for preparing cobalt acetate | |
| CN100415707C (en) | Method for preparing anchoic acid by microwave reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190809 |