CN108218710A - A kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste - Google Patents
A kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste Download PDFInfo
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- methyl benzoic
- benzoic acid
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- 238000006396 nitration reaction Methods 0.000 title claims abstract description 52
- 239000002910 solid waste Substances 0.000 title claims abstract description 49
- GPSDUZXPYCFOSQ-UHFFFAOYSA-N m-toluic acid Chemical compound CC1=CC=CC(C(O)=O)=C1 GPSDUZXPYCFOSQ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 24
- DGDAVTPQCQXLGU-UHFFFAOYSA-N 5437-38-7 Chemical compound CC1=CC=CC(C(O)=O)=C1[N+]([O-])=O DGDAVTPQCQXLGU-UHFFFAOYSA-N 0.000 claims abstract description 39
- QRRSIFNWHCKMSW-UHFFFAOYSA-N 5-methyl-2-nitrobenzoic acid Chemical compound CC1=CC=C([N+]([O-])=O)C(C(O)=O)=C1 QRRSIFNWHCKMSW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000000047 product Substances 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005352 clarification Methods 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- -1 3- methyl -4- nitrobenzoyl Chemical group 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- XXXOBNJIIZQSPT-UHFFFAOYSA-N 2-methyl-4-nitrobenzoic acid Chemical class CC1=CC([N+]([O-])=O)=CC=C1C(O)=O XXXOBNJIIZQSPT-UHFFFAOYSA-N 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000003232 p-nitrobenzoyl group Chemical group [N+](=O)([O-])C1=CC=C(C(=O)*)C=C1 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 43
- 239000000243 solution Substances 0.000 description 42
- XDTTUTIFWDAMIX-UHFFFAOYSA-N 3-methyl-4-nitrobenzoic acid Chemical class CC1=CC(C(O)=O)=CC=C1[N+]([O-])=O XDTTUTIFWDAMIX-UHFFFAOYSA-N 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000000428 dust Substances 0.000 description 6
- 230000000802 nitrating effect Effects 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000005711 Benzoic acid Substances 0.000 description 4
- 235000010233 benzoic acid Nutrition 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- CMUOJBJRZUHRMU-UHFFFAOYSA-N nitrourea Chemical compound NC(=O)N[N+]([O-])=O CMUOJBJRZUHRMU-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001815 facial effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QHDUJTCUPWHNPK-UHFFFAOYSA-N methyl 7-methoxy-2h-indazole-3-carboxylate Chemical compound COC1=CC=CC2=C(C(=O)OC)NN=C21 QHDUJTCUPWHNPK-UHFFFAOYSA-N 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RMMXLENWKUUMAY-UHFFFAOYSA-N telmisartan Chemical compound CCCC1=NC2=C(C)C=C(C=3N(C4=CC=CC=C4N=3)C)C=C2N1CC(C=C1)=CC=C1C1=CC=CC=C1C(O)=O RMMXLENWKUUMAY-UHFFFAOYSA-N 0.000 description 2
- YPQAFWHSMWWPLX-UHFFFAOYSA-N 1975-50-4 Chemical compound CC1=C(C(O)=O)C=CC=C1[N+]([O-])=O YPQAFWHSMWWPLX-UHFFFAOYSA-N 0.000 description 1
- HCUHAHONSFXZMF-UHFFFAOYSA-N 2-(2-carboxy-6-methylphenyl)-3-methylbenzoic acid Chemical compound CC1=CC=CC(C(O)=O)=C1C1=C(C)C=CC=C1C(O)=O HCUHAHONSFXZMF-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000005537 C09CA07 - Telmisartan Substances 0.000 description 1
- 239000005886 Chlorantraniliprole Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- IVTVGDXNLFLDRM-HNNXBMFYSA-N Tomudex Chemical compound C=1C=C2NC(C)=NC(=O)C2=CC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)S1 IVTVGDXNLFLDRM-HNNXBMFYSA-N 0.000 description 1
- YBOFEONRFJMHND-UHFFFAOYSA-N [Br].N#CC#N Chemical compound [Br].N#CC#N YBOFEONRFJMHND-UHFFFAOYSA-N 0.000 description 1
- AWPVYCXXUJPMOG-UHFFFAOYSA-N [N+](=O)(O)[O-].[S] Chemical compound [N+](=O)(O)[O-].[S] AWPVYCXXUJPMOG-UHFFFAOYSA-N 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000006172 aromatic nitration reaction Methods 0.000 description 1
- 230000036772 blood pressure Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- OOYGSFOGFJDDHP-KMCOLRRFSA-N kanamycin A sulfate Chemical group OS(O)(=O)=O.O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N OOYGSFOGFJDDHP-KMCOLRRFSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229960004432 raltitrexed Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229960005187 telmisartan Drugs 0.000 description 1
- TWSJLMGJCDXAFC-UHFFFAOYSA-N tetraphenylene-1,16-diol Chemical group C12=CC=CC=C2C2=CC=CC=C2C2=CC=CC(O)=C2C2=C1C=CC=C2O TWSJLMGJCDXAFC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste, include the following steps：(1) by m-methyl benzoic acid nitration reaction solid waste buck dissolved clarification, control solution pH value is 7.5~13, obtains clear solution；(2) it is 4.0 5.5 clear solution to be adjusted with acid solution pH value, obtains slurry, the first filtrate and the first filter cake is obtained by filtration, and the first filter cake with water is beaten and is filtered, obtains 3 methyl, 4 nitrobenzoyl acid product；(3) it is 2.5 4.0 the first filtrate to be adjusted with acid solution pH value, and the second filtrate and the second filter cake is obtained by filtration, and the second filter cake with water is beaten and is filtered, obtains 2 nitro, 3 methyl benzoic acid product；(4) it is 0 2.5 the second filtrate to be adjusted with acid solution pH value, and third filtrate and third filter cake is obtained by filtration, and third filter cake with water is beaten and is filtered, obtains 2 nitro, 5 methyl benzoic acid product.The present invention is simple with method, easily operated, of low cost, and especially having turns waste into wealth, conducive to environmentally friendly significance.
Description
Technical field
The present invention relates to fine chemical technology and field of environment protection, more particularly to a kind of m-methyl benzoic acid nitration reaction solid waste
Method of comprehensive utilization.
Background technology
2- nitro -3- methyl benzoic acids are the core starting originals of production weight pound insecticide chlorantraniliprole and bromine cyanogen insect amide
Material.Its industrial process is using m-methyl benzoic acid as raw material, is made through nitric acid or mixed sulphur nitric acid for nitrating agent, the change of generation
Learning reaction is：
Typical open source information report result is listed below：
(the Urea nitrate and nitrourea.Powerful and regioselective such as Almog
aromatic nitration agents.From Tetrahedron Letters,47(49),8651-8652；2006) it uses
The mixture of urea nitrate or nitrourea and sulfuric acid is nitrating agent.When being nitrating agent with nitro urea+concentrated sulfuric acid, first
The selectivity of 2,4 and 6 substitution products of acid nitrification is 23 between base benzene:3:74, the i.e. selectivity of 2- nitros -3- methyl benzoic acids
Only 23%；When being nitrating agent with nitrourea+concentrated sulfuric acid, the selection of 2,4 and 6 substitution products of acid nitrification between methylbenzene
Property is 22:12:58, i.e. the selectivity of 2- nitros -3- methyl benzoic acids is only 22%.Further, which substantially still falls within
Mixing sulfuric acid and nitric acid are digested for nitrating agent, a large amount of mixing spent acid can be generated in subsequent processing procedure, it is difficult to recycle
It utilizes, easily causes environmental pollution.
(A significant improvement the in enantioselectivity, yield, and such as Samadi
reactivity for the copper-bi-o-tolyl bisoxazoline-catalyzed asymmetric
allylic oxidation of cyclic olefins using recoverable SBA-15mesoporous silica
material.From Tetrahedron,69(32),6679-6686；2013) building-up process of report is as follows：Methylbenzene between 1g
Formic acid is slowly added into the fuming nitric aicd that 4mL is stirred continuously, and maintains -10 DEG C of temperature, is reacted 1 hour.TLC tracking react into
Degree, filters reaction mixture, obtains 2- methyl-3-nitro benzoic acid crude products, then washed with cold water, obtain 2- first after reaction
Base -3- nitrobenzoic acid 0.66g, yield 50%.(the Mimicry of the 2-His-1-Carboxylate such as Folkertsma
Facial Triad Using Bulky N,N,O-Ligands:Non-Heme Iron Complexes Featuring a
Single Facial Ligand and Easily Exchangeable Co-Ligands.From European Journal
of Inorganic Chemistry,2016(9),1319-1332；2016) same method, yield 42% are employed.Wen etc.
(Synthesis,Resolution,and Applications of 1,16-Dihydroxytetraphenylene as a
Novel Building Block in Molecular Recognition and Assembly By et al.From
Journal of Organic Chemistry,68(23),8918-8931；2003) same method, yield 46% are employed.
(the Conformational behavior of medium-sized rings.Part such as Guise
10.Dithiosalicylides and trithiosalicylides.From Journal of the Chemical
Society,Perkin Transactions 1:Organic and Bio-Organic Chemistry(1972-1999),
(8),1637-48；1982) same method, yield 38% are employed.
(the Practical method for the synthesis and optical resolution of such as Kano
axially dissymmetric 6,6'-dimethylbiphenyl-2,2'-dicarboxylic acid.From
Bulletin of the Chemical Society of Japan,60(10),3659-62；1987) using N2O5And HNO3's
Mixture is nitrating agent, has carried out the nitrification of m-methyl benzoic acid as aforementioned report, 2- nitro -3- methyl benzoic acids
Yield is compared with only 49%.
In summary, it is known that：The nitration method of existing m-methyl benzoic acid, product selection more there are nitration by-products
The low deficiency of property.To existing industrial production, by existing technology in this field data, by highest 2- nitros -3- methyl benzoic acids
Yield 50% calculates, and often produces 1 ton of target product, will generate at least 1 ton of nitration by-products, will be burned as solid waste
Processing.Through analysis, the nitration reaction solid waste main component of m-methyl benzoic acid is the isomerism of various methyl nitrobenzoic acids
Body, the i.e. predominantly mixing of 2- nitros -3- methyl benzoic acids, 3- methyl -4- nitrobenzoic acids and 2- nitro -5- methyl benzoic acids
Object.3- methyl -4- nitrobenzoic acids are the core starting materials for the first-line drug Telmisartan for producing clinically blood pressure lowering, 2- nitre
Base -5- methylbenzene first is also to produce the core starting material of a variety of important drugs, such as celeste, Raltitrexed, is respectively provided with
Certain economic value.
Under the increasingly serious new model of environmental requirement, a kind of nitration reaction for the m-methyl benzoic acid being simple and efficient is found
The method of comprehensive utilization of solid waste therefrom recycles useful component 2- nitro -3- methyl benzoic acids, 3- methyl -4- nitre as far as possible
Yl benzoic acid and 2- nitro -5- methyl benzoic acids just become extremely urgent, have extremely strong environment protection significance and economic benefit.
Invention content
The object of the present invention is to provide a kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste, therefrom high receipts
Recycling 2- nitro -3- methyl benzoic acids, 3- methyl -4- nitrobenzoic acids and the 2- nitro -5- methyl benzoic acids of rate, it is useless so as to become
For treasured.
To achieve the above object, the technical solution adopted by the present invention is that：A kind of m-methyl benzoic acid nitration reaction solid waste
Method of comprehensive utilization includes the following steps：
(1) by m-methyl benzoic acid nitration reaction solid waste buck dissolved clarification, control solution pH value is 7.5~13, is obtained clear
Clear solution；
(2) clear solution that step (1) obtains is adjusted with acid solution pH value as 4.0-5.5, obtains slurry, be obtained by filtration
First filter cake with water is beaten and filtered, obtains 3- methyl -4- nitrobenzoyl acid products by the first filtrate and the first filter cake；
(3) the first filtrate that step (2) obtains is adjusted with acid solution pH value as 2.5-4.0, the second filtrate is obtained by filtration
With the second filter cake, the second filter cake with water is beaten and is filtered, obtains 2- nitro -3- methyl benzoic acid products；
(4) the second filtrate that step (3) obtains is adjusted with acid solution pH value as 0-2.5, be obtained by filtration third filtrate and
Third filter cake with water is beaten and filtered, obtains 2- nitro -5- methyl benzoic acid products by third filter cake.
As the preferred embodiment of the present invention, 2- nitro -3- first in the m-methyl benzoic acid nitration reaction solid waste
The mass percentage of yl benzoic acid is preferably that the mass percentage of 10~50%, 3- methyl -4- nitrobenzoic acids is preferably
10~60%, the mass percentage of 2- nitros -5- methyl benzoic acids is preferably 20~70%.
As the preferred embodiment of the present invention, the acid be preferably one kind in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or
A variety of mixtures.
As the preferred embodiment of the present invention, the alkali is preferably NaOH, Na2CO3、NaHCO3、KOH、K2CO3、
KHCO3In one or more mixtures.
Three kinds of isomers that m-methyl benzoic acid nitrifies, i.e. 2- nitros -3- methyl benzoic acids, 3- methyl -4-
Nitrobenzoic acid and 2- nitro -5- methyl benzoic acids, molecular formula is C8H7O4N, molecular weight are 181.15.Its fundamental property
It is as shown in the table：
It is found that the fusing point and boiling point of three kinds of methyl nitrobenzoic acids are all very high, and boiling point is very close to conventional same point different
The separation method of structure body, such as rectification method are not suitable for the separation of this mixture system.Meanwhile inventor tests by a large amount of,
Carefully studied solubility of the above-mentioned three kinds of isomer acid in different solvents, the solvent of research cover organic acid, ester,
Alcohol, ether, ketone, water etc., related work refer to (1.Xiaojun He, Ze Tan, Qinbo Wang*, and Yinchuan
Pei.Study on the Solubilities of Mononitro-Substituted Products of Nitration
of m-Toluic Acid in Several Solvents at Temperatures between 297.65 and
351.75 K.J.Chem.Eng.Data 2017,62,3360-3367；2. Pei Yinchuan, the solubility of methyl nitrobenzoic acid is surveyed
Determine with being associated with.Hunan University's master thesis, 2016.5.).Based on this, inventor has carried out systematic research, further sends out
It is existing, although three kinds of isomers of methyl nitrobenzoic acid equal very little of solubility in water, suitably adjusts solution PH, energy
Dissolving a certain kind of selectivity or a variety of methyl nitrobenzoic acids.The adjusting of pH value must be according to sequence from big to small, ability
Carry out the separation of above-mentioned three kinds of isomers, if the adjusting of pH value according to sequence from small to large, cannot be by above-mentioned three kinds
Isomer is detached.Based on this, the present invention does not add organic solvent, directly in water by adjusting solution pH value by between
The method that the isomer that the nitrification of methyl benzoic acid obtains is detached, it is so as to reach that the nitrification of m-methyl benzoic acid is anti-
Solid waste is answered to be comprehensively utilized, the purpose to turn waste into wealth.
According to the present invention, the key component of nitration reaction solid waste is 2- nitro -5- methyl benzoic acids, 2- nitro -3- methyl
Benzoic acid and 3- methyl -4- nitrobenzoic acids.
The definition for characterizing the rate of recovery of each product is：
The quality of 3- methyl -4- nitrobenzoic acids that 3- methyl -4- nitrobenzoic acids=step (2) obtains/input reaction
The nitration reaction solid waste quality of device.It is expressed as a percentage in embodiment.
The quality of 2- nitro -3- methyl benzoic acids that 2- nitros -3- methyl benzoic acids=step (3) obtains/input reaction
The nitration reaction solid waste quality of device.It is expressed as a percentage in embodiment.
The quality of 2- nitro -5- methyl benzoic acids that the rate of recovery=step (4) of 2- nitro -5- methyl benzoic acids obtains/
Put into the nitration reaction solid waste quality in reactor.It is expressed as a percentage in embodiment.
Compared with prior art, the invention has the advantages that：
1st, method is simple, easily operated.Organic solvent is not added, directly in water by adjusting solution pH value methyl by between
The isomer that benzoic acid nitrifies is detached, and method is simple, easily operated.
2nd, environment protecting is apparent.By this field, highest 2- nitros -3- methyl benzoic acids yield 50% calculates at present, often leads to
The nitration reaction for crossing m-methyl benzoic acid produces 1 ton of target product 2- nitro -3- methyl benzoic acid, will generate 1 ton of nitrification pair
Product will be used as solid waste to carry out burning disposal.After method of the present invention, in nitration by-products per ton, it can recycle
Total rate of recovery of 2- nitro -3- methyl benzoic acids, 3- methyl -4- nitrobenzoic acids and 2- nitro -5- methyl benzoic acids surpasses
Cross 80%, up to 89.8%, it is meant that often by the nitration reaction of m-methyl benzoic acid produce 1 ton of target product 2- nitro-
3- methyl benzoic acids, the amounts of the nitration by-products of generation are reduced to 200 kilograms hereinafter, the amount of solid waste reduces more than 80%, ring
It protects with obvious effects.
3rd, remarkable in economical benefits.It is often anti-by the nitrification of m-methyl benzoic acid while significant environmental benefit is obtained
1 ton of target product 2- nitro -3- methyl benzoic acid should be produced, more than 80% 2- nitro -3- first has been recycled from nitrification solid waste
Yl benzoic acid, 3- methyl -4- nitrobenzoic acids and 2- nitro -5- methyl benzoic acids, these three methyl nitrobenzoic acids are being cured
Medicine and pesticide field have important use, and economic value is apparent, and realizing turns waste into wealth, remarkable in economical benefits.
Specific embodiment
The comprehensive utilization flow of the m-methyl benzoic acid nitration reaction solid waste of the present invention is as follows：
(1) 200g m-methyl benzoic acid nitration reaction solid wastes is taken to be added in four mouthfuls of vials of a 1000ml, alkali is added dropwise
Liquid makes nitration reaction solid waste dissolved clarification, and control solution PH obtains clear solution 7.5~13；
(2) acid is slowly added dropwise into the clear solution that step (1) obtains and stirs, adjust solution pH value in 4.0-5.5, analysis
Go out a large amount of solids, obtain slurry, the first filtrate and the first filter cake is obtained by filtration, the first filter cake with water is beaten and is filtered, obtains matter
Measure the 3- methyl -4- nitrobenzoyl acid products of more than 99% percentage composition；
(3) into the first filtrate that step (2) obtains continue that acid is slowly added dropwise and stir, adjust solution pH value in 2.5-
4.0, a large amount of solids are precipitated, the second filtrate and the second filter cake is obtained by filtration, the second filter cake with water is beaten and is filtered, obtains quality hundred
Divide the 2- nitro -3- methyl benzoic acid products of more than 98% content；
(4) into the second filtrate that step (3) obtains continue that acid is slowly added dropwise and stir, adjust solution pH value in 0-2.5,
A large amount of solids are precipitated, third filtrate and third filter cake is obtained by filtration, third filter cake with water is beaten and is filtered, quality percentage is obtained and contains
2- nitro -5- methyl benzoic acid the products of more than 98% amount；
The present invention is described in further detail with reference to embodiments, but the present invention is not limited to the embodiment described.
Embodiment 1
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
10%th, 3- methyl -4- nitrobenzoic acids mass percentage 28%, 2- nitro -5- methyl benzoic acids mass percentage 62%.
The NaOH aqueous solutions of step (1) use quality percent concentration 30% are by nitration reaction solid waste dissolved clarification, final PH=12.8.Step
(2) 25% concentrated hydrochloric acid of use quality percent concentration adjusts solution PH=4.4, obtains 3- methyl -4- nitrobenzoic acids
51.8g, the rate of recovery 92.6%.Step (3) use quality percent concentration 25% concentrated hydrochloric acid adjusts solution PH=3.2, obtains
2- nitro -3- methyl benzoic acid 18.3g, the rate of recovery 91.5%.Step (4) use quality percent concentration 25% concentrated hydrochloric acid is adjusted
Solution PH=1.2 are saved, obtain 2- nitro -5- methyl benzoic acid 96.3g, the rate of recovery 77.7%., total rate of recovery of three is
83.2%.
Embodiment 2
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
15%th, 3- methyl -4- nitrobenzoic acids mass percentage 20%, 2- nitro -5- methyl benzoic acids mass percentage 65%.
The KOH aqueous solutions of step (1) use quality percent concentration 20% are by nitration reaction solid waste dissolved clarification, final PH=8.4.Step
(2) 10% dust technology of use quality percent concentration adjusts solution PH=4.0, obtains 3- methyl -4- nitrobenzoic acids
36.8g, the rate of recovery 92.0%.Step (3) use quality percent concentration 10% dust technology adjusts solution PH=2.5, obtains
2- nitro -3- methyl benzoic acid 28.5g, the rate of recovery 95.0%.Step (4) use quality percent concentration 10% dust technology is adjusted
Solution PH=0.5 is saved, obtains 2- nitro -5- methyl benzoic acid 94.9g, the rate of recovery 73.0%., total rate of recovery of three is
80.1%.
Embodiment 3
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
20%th, 3- methyl -4- nitrobenzoic acids mass percentage 10%, 2- nitro -5- methyl benzoic acids mass percentage 70%.
The NaHCO of step (1) use quality percent concentration 15%3Aqueous solution is by nitration reaction solid waste dissolved clarification, final PH=7.5.Step
Suddenly 50% phosphoric acid of (2) use quality percent concentration adjusts solution PH=5.5, obtains 3- methyl -4- nitrobenzoic acids
19.1g, the rate of recovery 95.4%.Step (3) use quality percent concentration 50% phosphoric acid adjusts solution PH=4.0, obtains 2-
Nitro -3- methyl benzoic acid 36.2g, the rate of recovery 90.5%.50% phosphoric acid of step (4) use quality percent concentration is molten to adjust
Liquid PH=2.4 obtains 2- nitro -5- methyl benzoic acid 116.2g, the rate of recovery 83.0%., total rate of recovery of three is
85.7%.
Embodiment 4
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
25%th, 3- methyl -4- nitrobenzoic acids mass percentage 18%, 2- nitro -5- methyl benzoic acids mass percentage 57%.
The KHCO of step (1) use quality percent concentration 12%3Aqueous solution is by nitration reaction solid waste dissolved clarification, final PH=7.9.Step
(2) 95% sulfuric acid of use quality percent concentration adjusts solution PH=4.5, obtains 3- methyl -4- nitrobenzoic acid 33.5g,
The rate of recovery 93.1%.Step (3) use quality percent concentration 95% sulfuric acid adjusts solution PH=3.4, obtains 2- nitros -3-
Methyl benzoic acid 45.3g, the rate of recovery 90.5%.95% sulfuric acid of step (4) use quality percent concentration come adjust solution PH=
1.6, obtain 2- nitro -5- methyl benzoic acid 91.6g, the rate of recovery 80.3%., total rate of recovery of three is 85.2%.
Embodiment 5
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
30%th, 3- methyl -4- nitrobenzoic acids mass percentage 22%, 2- nitro -5- methyl benzoic acids mass percentage 48%.
The K of step (1) use quality percent concentration 15%2CO3Aqueous solution is by nitration reaction solid waste dissolved clarification, final PH=7.5.Step
(2) 35% sulfuric acid of use quality percent concentration adjusts solution PH=4.4, obtains 3- methyl -4- nitrobenzoic acid 40.7g,
The rate of recovery 92.6%.Step (3) use quality percent concentration 35% sulfuric acid adjusts solution PH=3.2, obtains 2- nitros -3-
Methyl benzoic acid 54.9g, the rate of recovery 91.5%.95% sulfuric acid of step (4) use quality percent concentration come adjust solution PH=
1.1, obtain 2- nitro -5- methyl benzoic acid 73.9g, the rate of recovery 77.0%., total rate of recovery of three is 84.8%.
Embodiment 6
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
35%th, 3- methyl -4- nitrobenzoic acids mass percentage 15%, 2- nitro -5- methyl benzoic acids mass percentage 50%.
The Na of step (1) use quality percent concentration 10%2CO3Aqueous solution is by nitration reaction solid waste dissolved clarification, final PH=7.7.Step
(2)+10% dust technology of 15% dilute hydrochloric acid of use quality percent concentration adjusts solution PH=4.9, obtains 3- methyl -4- nitros
Benzoic acid 27.8g, the rate of recovery 92.6%.Step (3) 15% dilute hydrochloric acid of use quality percent concentration+10% dust technology is adjusted
Solution PH=2.9 obtain 2- nitro -3- methyl benzoic acid 65.1g, the rate of recovery 93.0%.Step (4) use quality percentage is dense
+ 10% dust technology of 15% dilute hydrochloric acid is spent to adjust solution PH=0.7, obtains 2- nitro -5- methyl benzoic acid 74.3g, the rate of recovery
74.3%., total rate of recovery of three is 83.6%.
Embodiment 7
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
40%th, 3- methyl -4- nitrobenzoic acids mass percentage 21%, 2- nitro -5- methyl benzoic acids mass percentage 39%.
The NaOH+10%KOH aqueous solutions of step (1) use quality percent concentration 30% are by nitration reaction solid waste dissolved clarification, final PH=
11.1.Step (2) use quality percent concentration 20% hydrochloric acid adjusts solution PH=4.4, obtains 3- methyl -4- nitrobenzoyls
Sour 38.9g, the rate of recovery 92.6%.Step (3) use quality percent concentration 20% hydrochloric acid adjusts solution PH=2.8, obtains
2- nitro -3- methyl benzoic acid 74.8g, the rate of recovery 93.5%.Step (4) use quality percent concentration 20% hydrochloric acid is adjusted
Solution PH=1.0 obtain 2- nitro -5- methyl benzoic acid 59.5g, the rate of recovery 76.3%., total rate of recovery of three is
86.6%.
Embodiment 8
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
45%th, 3- methyl -4- nitrobenzoic acids mass percentage 25%, 2- nitro -5- methyl benzoic acids mass percentage 30%.
The NaOH aqueous solutions of step (1) use quality percent concentration 25% are by nitration reaction solid waste dissolved clarification, final PH=9.8.Step
(2) 25% dilute sulfuric acid of use quality percent concentration adjusts solution PH=4.7, obtains 3- methyl -4- nitrobenzoic acids
47.1g, the rate of recovery 94.3%.Step (3) use quality percent concentration 20% hydrochloric acid adjusts solution PH=3.8, obtains 2-
Nitro -3- methyl benzoic acid 81.5g, the rate of recovery 90.5%.20% hydrochloric acid of step (4) use quality percent concentration is molten to adjust
Liquid PH=2.0 obtains 2- nitro -5- methyl benzoic acid 48.6g, the rate of recovery 81.0%., total rate of recovery of three is
88.6%.
Embodiment 9
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
50%th, 3- methyl -4- nitrobenzoic acids mass percentage 30%, 2- nitro -5- methyl benzoic acids mass percentage 20%.
The NaOH aqueous solutions of step (1) use quality percent concentration 25% are by nitration reaction solid waste dissolved clarification, final PH=8.4.Step
(2) 25% dilute sulfuric acid of use quality percent concentration adjusts solution PH=4.5, obtains 3- methyl -4- nitrobenzoic acids
55.9g, the rate of recovery 93.1%.Step (3) use quality percent concentration 20% hydrochloric acid adjusts solution PH=3.0, obtains 2-
Nitro -3- methyl benzoic acid 92.5g, the rate of recovery 92.5%.20% hydrochloric acid of step (4) use quality percent concentration is molten to adjust
Liquid PH=0 obtains 2- nitro -5- methyl benzoic acid 31.1g, the rate of recovery 77.7%., total rate of recovery of three is 89.7%.
Embodiment 10
The composition of the nitration reaction solid waste of m-methyl benzoic acid is：2- nitro -3- methyl benzoic acid mass percentages
13%th, 3- methyl -4- nitrobenzoic acids mass percentage 57%, 2- nitro -5- methyl benzoic acids mass percentage 30%.
The NaOH aqueous solutions of step (1) use quality percent concentration 25% are by nitration reaction solid waste dissolved clarification, final PH=7.9.Step
(2) 25% dilute sulfuric acid of use quality percent concentration adjusts solution PH=4.6, obtains 3- methyl -4- nitrobenzoic acids
106.8g the rate of recovery 93.7%.Step (3) use quality percent concentration 20% hydrochloric acid adjusts solution PH=3.2, obtains 2-
Nitro -3- methyl benzoic acid 23.8g, the rate of recovery 91.5%.20% hydrochloric acid of step (4) use quality percent concentration is molten to adjust
Liquid PH=1.8 obtains 2- nitro -5- methyl benzoic acid 49.0g, the rate of recovery 81.7%., total rate of recovery of three is
89.8%.
Claims (4)
1. a kind of method of comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste, which is characterized in that include the following steps：
(1) by m-methyl benzoic acid nitration reaction solid waste buck dissolved clarification, control solution pH value is 7.5~13, obtains clarifying molten
Liquid；
(2) clear solution that step (1) obtains is adjusted with acid solution pH value as 4.0-5.5, obtains slurry, be obtained by filtration first
First filter cake with water is beaten and filtered, obtains 3- methyl -4- nitrobenzoyl acid products by filtrate and the first filter cake；
(3) the first filtrate that step (2) obtains is adjusted with acid solution pH value as 2.5-4.0, the second filtrate and the is obtained by filtration
Second filter cake with water is beaten and filtered, obtains 2- nitro -3- methyl benzoic acid products by two filter cakes；
(4) the second filtrate that step (3) obtains is adjusted with acid solution pH value as 0-2.5, third filtrate and third is obtained by filtration
Third filter cake with water is beaten and filtered, obtains 2- nitro -5- methyl benzoic acid products by filter cake.
2. the method for comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste according to claim 1, which is characterized in that institute
The mass percentage of 2- nitro -3- methyl benzoic acids is 10~50%, 3- in the m-methyl benzoic acid nitration reaction solid waste stated
The mass percentage of methyl -4- nitrobenzoic acids is 10~60%, the mass percentage of 2- nitro -5- methyl benzoic acids is
20~70%.
3. the method for comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste according to claim 1, which is characterized in that institute
The acid stated is hydrochloric acid, one or more mixtures in sulfuric acid, nitric acid, phosphoric acid.
4. the method for comprehensive utilization of m-methyl benzoic acid nitration reaction solid waste according to claim 1, which is characterized in that institute
The alkali stated is NaOH, Na2CO3、NaHCO3、KOH、K2CO3、KHCO3In one or more mixtures.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111807963A (en) * | 2020-08-07 | 2020-10-23 | 山东友道化学有限公司 | Green nitration treatment method of m-toluic acid |
| CN111995523A (en) * | 2020-09-09 | 2020-11-27 | 南京鹳山化工科技有限公司 | Resource utilization method of nitrobenzoic acid derivative waste acid liquor |
| CN112441907A (en) * | 2019-08-30 | 2021-03-05 | 山东有言环保科技有限公司 | Method for co-producing mono-substituted methyl benzoic acid and mono-substituted phthalic acid |
| CN112441926A (en) * | 2019-08-30 | 2021-03-05 | 山东有言环保科技有限公司 | Method for co-producing m-methylbenzoic acid nitride and m-phthalic acid |
Citations (1)
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| CN106496038A (en) * | 2016-11-01 | 2017-03-15 | 安徽安生生物化工科技有限责任公司 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106496038A (en) * | 2016-11-01 | 2017-03-15 | 安徽安生生物化工科技有限责任公司 | A kind of preparation method of 3 methyl, 2 nitrobenzoic acid of high selectivity |
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| CN112441907A (en) * | 2019-08-30 | 2021-03-05 | 山东有言环保科技有限公司 | Method for co-producing mono-substituted methyl benzoic acid and mono-substituted phthalic acid |
| CN112441926A (en) * | 2019-08-30 | 2021-03-05 | 山东有言环保科技有限公司 | Method for co-producing m-methylbenzoic acid nitride and m-phthalic acid |
| CN112441926B (en) * | 2019-08-30 | 2022-10-14 | 山东友道化学有限公司 | Method for co-producing m-methylbenzoic acid nitride and m-phthalic acid |
| CN112441907B (en) * | 2019-08-30 | 2023-10-31 | 山东友道化学有限公司 | Method for co-producing mono-substituted methylbenzoic acid and mono-substituted phthalic acid |
| CN111807963A (en) * | 2020-08-07 | 2020-10-23 | 山东友道化学有限公司 | Green nitration treatment method of m-toluic acid |
| CN111807963B (en) * | 2020-08-07 | 2022-11-18 | 山东友道化学有限公司 | Green nitration treatment method of m-methylbenzoic acid |
| CN111995523A (en) * | 2020-09-09 | 2020-11-27 | 南京鹳山化工科技有限公司 | Resource utilization method of nitrobenzoic acid derivative waste acid liquor |
| CN111995523B (en) * | 2020-09-09 | 2023-06-16 | 南京鹳山化工科技有限公司 | Resource utilization method of waste acid liquid of nitrobenzoic acid derivatives |
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