CN114716298A - Environment-friendly benzene chloride production process - Google Patents
Environment-friendly benzene chloride production process Download PDFInfo
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- CN114716298A CN114716298A CN202210210545.XA CN202210210545A CN114716298A CN 114716298 A CN114716298 A CN 114716298A CN 202210210545 A CN202210210545 A CN 202210210545A CN 114716298 A CN114716298 A CN 114716298A
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000002156 mixing Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000460 chlorine Substances 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 11
- 239000006249 magnetic particle Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005660 chlorination reaction Methods 0.000 abstract description 10
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 abstract description 4
- 229940117389 dichlorobenzene Drugs 0.000 abstract description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 208000005156 Dehydration Diseases 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 244000144725 Amygdalus communis Species 0.000 description 1
- 235000003893 Prunus dulcis var amara Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to an environment-friendly chlorobenzene production process, which belongs to the technical field of organic synthesis and comprises the following steps: firstly, carrying out anhydrous treatment on industrial pure benzene to obtain anhydrous benzene for later use; secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 80-90 ℃, reacting for 1-1.5h, and after the reaction is finished, carrying out post-treatment on the obtained reaction liquid to obtain benzene chloride; the prepared additive, the acrylic acid and the acrylamide are compounded to be used as an adsorption material for dehydration treatment, through tests, the water content in pure benzene can be controlled below 100ppm, the water content in chlorination reaction is reduced, the consumption of iron rings is reduced, and 200 tons of iron rings are saved every year; the impurity content of dichlorobenzene in the chlorination reaction is reduced, and the content of dichlorobenzene is reduced by 2.5 percent; the chlorination reaction moisture is reduced, the amount of generated ferric trichloride is reduced, the washing times are reduced, and the method is more environment-friendly.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an environment-friendly chlorobenzene production process.
Background
Chlorobenzene, also called chlorobenzene, is a colorless, transparent, volatile liquid with the flavor of bitter almonds. Melting point-45.6 deg.C, boiling point 131.6 deg.C, relative density 1.107(20/4 deg.C), refractive index 1.5248, flash point 23 deg.C, spontaneous combustion point 637.78 deg.C, and flammability. The explosive limit in air is 1.83-9.23% (by volume). It is insoluble in water and soluble in alcohol, ether, benzene, chloroform, etc. The chlorobenzene is an important basic organic synthetic raw material and is used as a dye, medicine, pesticide and organic synthetic intermediate.
At present, commonly used catalysts for benzene chlorination are lewis acid catalysts such as ferric trichloride and the like, and the catalysts are easily dissolved in a reaction liquid, so that the chlorination reaction liquid needs to be washed, neutralized and the like to remove the catalysts, so that the catalysts are not only consumed at one time, but also the process is complicated, a large amount of waste water and waste residues are generated, and the environment is greatly polluted. As known from the reaction mechanism, hydrogen chloride is generated in the chlorination process of benzene, if the water content is high, the hydrogen chloride is dissolved in water to generate more hydrochloric acid, the hydrochloric acid reacts with the iron ring violently to generate hydrogen and iron dichloride, and the hydrochloric acid and the oxygen generated by the reaction of the chlorine and the water not only consume the chlorine but also 'eat' the iron ring, but also the large amount of the iron dichloride influences the chlorination reaction, and the generated hydrogen and the oxygen also increase unsafe factors of the system.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides an environment-friendly chlorinated benzene production process.
The purpose of the invention can be realized by the following technical scheme:
an environment-friendly chlorobenzene production process comprises the following steps:
firstly, carrying out anhydrous treatment on industrial pure benzene to obtain anhydrous benzene for later use;
and secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 80-90 ℃, reacting for 1-1.5h, after the reaction is finished, washing the obtained reaction liquid, neutralizing the washed solution with ammonia water, extracting with anhydrous benzene, and concentrating the organic phase under reduced pressure to obtain the chlorobenzene.
Further, the anhydrous treatment comprises the following steps:
mixing the adsorbing material and industrial pure benzene, mixing for 10-12h at 30 ℃, and then filtering under the condition of a magnetic field to obtain anhydrous benzene.
Further, the adsorbing material is prepared by the following steps:
dropwise adding a sodium carbonate solution into acrylic acid until the neutralization degree is 80%, then adding acrylamide, potassium persulfate and a cross-linking agent, stirring for 5min after adding, adding an additive, uniformly mixing, freezing for 12h at-10 ℃, taking out after freezing, adding span-80 and cyclohexane, stirring for 1h at 45 ℃, then heating to 70 ℃, stirring for 4h, filtering the obtained reaction solution after the reaction is finished, washing a filter cake with absolute ethyl alcohol, drying in vacuum to constant weight at 80 ℃ after the washing is finished, crushing, sieving with a 20-mesh sieve, and activating for 3-4h at 350 ℃ to obtain the adsorbing material.
Further, the mass fraction of the sodium carbonate solution is 13%, and the mass ratio of the acrylic acid, the acrylamide, the potassium persulfate, the cross-linking agent and the additive is 100: 30: 0.2: 0.04: 7-8; the mass ratio of the acrylic acid to the span-80 to the cyclohexane is 1: 0.02: 1; the cross-linking agent is one of N, N-methylene bisacrylamide and diethylenetriamine.
Further, the additive is prepared by the following steps:
mixing chitosan and acetic acid solution, adding magnetic ferroferric oxide, stirring for 1h, adding 4,4 '-dicyclohexylmethane diisocyanate and stannous octoate, stirring for 2h, filtering, washing, filtering and drying to obtain magnetic particles, taking the 4,4' -dicyclohexylmethane diisocyanate as a cross-linking agent, immobilizing the magnetic ferroferric oxide on the chitosan to facilitate subsequent reaction, mixing MCM-41 and dimethyl sulfoxide, adding the magnetic particles, adding stannous octoate, stirring for 2h at 25 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and freeze-drying after the washing is finished to obtain the additive.
Further, the mass fraction of the acetic acid solution is 2%, and the dosage ratio of the chitosan to the acetic acid solution is 0.2 g: 50 mL; the dosage ratio of the chitosan, the magnetic ferroferric oxide, the 4,4' -dicyclohexylmethane diisocyanate and the stannous octoate is 0.2 g: 0.1 g: 0.2 mL: 0.06 g; the use ratio of MCM-41, dimethyl sulfoxide, magnetic particles and stannous octoate is 0.2 g: 50mL of: 0.2 g: 0.06 g.
Further, the mass fraction of ammonia water used for neutralization is 20-30%.
Further, the temperature is set to 20-30 ℃ during water washing.
The invention has the beneficial effects that:
the environment-friendly chlorobenzene production process utilizes the prepared additive to be compounded with acrylic acid and acrylamide to be used as an adsorption material to carry out dehydration treatment, through tests, the water content in pure benzene can be controlled below 100ppm, the water content in chlorination reaction is reduced, the consumption of iron rings is reduced, and 200 tons of benzene is saved every year; the impurity content of dichlorobenzene in the chlorination reaction is reduced, and the content of dichlorobenzene is reduced by 2.5 percent. The chlorination reaction moisture is reduced, the amount of generated ferric trichloride is reduced, the washing times are reduced, and the method is more environment-friendly. In the prepared additive, MCM-41 has porosity, the surface of the pore wall has rich silanol hydroxyl, the MCM-41 is fixed on the magnetic particles by utilizing the coupling effect of chitosan to prepare the additive, and the addition of the MCM-41 can improve the removal efficiency of trace water.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing an additive:
mixing chitosan and acetic acid solution, adding magnetic ferroferric oxide, stirring for 1h, adding 4,4' -dicyclohexylmethane diisocyanate and stannous octoate, stirring for 2h, filtering, washing, filtering and drying to obtain magnetic particles, mixing MCM-41 and dimethyl sulfoxide, adding magnetic particles, adding stannous octoate, stirring for 2h at 25 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and freeze-drying to obtain the additive after the washing is finished. Controlling the mass fraction of the acetic acid solution to be 2%, and controlling the dosage ratio of the chitosan to the acetic acid solution to be 0.2 g: 50 mL; the dosage ratio of the chitosan, the magnetic ferroferric oxide, the 4,4' -dicyclohexylmethane diisocyanate and the stannous octoate is 0.2 g: 0.1 g: 0.2 mL: 0.06 g; the use ratio of MCM-41, dimethyl sulfoxide, magnetic particles and stannous octoate is 0.2 g: 50mL of: 0.2 g: 0.06 g.
Example 2
Preparing an adsorbing material:
dropwise adding a sodium carbonate solution into acrylic acid until the neutralization degree is 80%, then adding acrylamide, potassium persulfate and a cross-linking agent, stirring for 5min after adding, adding an additive, uniformly mixing, freezing for 12h at-10 ℃, taking out after freezing, adding span-80 and cyclohexane, stirring for 1h at 45 ℃, then heating to 70 ℃, stirring for 4h, filtering the obtained reaction solution after the reaction is finished, washing a filter cake with absolute ethyl alcohol, drying in vacuum to constant weight at 80 ℃ after the washing is finished, crushing, sieving with a 20-mesh sieve, and activating for 3h at 350 ℃ to obtain the adsorbing material. Controlling the mass fraction of the sodium carbonate solution to be 13%, and controlling the mass ratio of the acrylic acid, the acrylamide, the potassium persulfate, the cross-linking agent and the additive to be 100: 30: 0.2: 0.04: 7; the mass ratio of the acrylic acid to the span-80 to the cyclohexane is 1: 0.02: 1; the cross-linking agent is N, N-methylene bisacrylamide.
Example 3
Preparing an adsorbing material:
dropwise adding a sodium carbonate solution into acrylic acid until the neutralization degree is 80%, then adding acrylamide, potassium persulfate and a cross-linking agent, stirring for 5min after adding, adding an additive, uniformly mixing, freezing for 12h at-10 ℃, taking out after freezing, adding span-80 and cyclohexane, stirring for 1h at 45 ℃, then heating to 70 ℃, stirring for 4h, filtering the obtained reaction solution after the reaction is finished, washing a filter cake with absolute ethyl alcohol, drying in vacuum to constant weight at 80 ℃ after the washing is finished, crushing, sieving with a 20-mesh sieve, and activating for 4h at 350 ℃ to obtain the adsorbing material. Controlling the mass fraction of the sodium carbonate solution to be 13%, and controlling the mass ratio of the acrylic acid, the acrylamide, the potassium persulfate, the cross-linking agent and the additive to be 100: 30: 0.2: 0.04: 8; the mass ratio of the acrylic acid to the span-80 to the cyclohexane is 1: 0.02: 1; the crosslinking agent is diethylenetriamine.
Example 4
An environment-friendly chlorobenzene production process comprises the following steps:
step one, mixing the adsorbing material prepared in the embodiment 3 with industrial pure benzene, mixing for 10 hours at the temperature of 30 ℃, and then filtering under the condition of a magnetic field to obtain anhydrous benzene for later use;
and secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 80 ℃, reacting for 1h, washing the obtained reaction liquid at the temperature of 20 ℃, neutralizing the washed solution by ammonia water with the mass fraction of 20% after the reaction is finished, extracting by anhydrous benzene, and concentrating the organic phase under reduced pressure to obtain the chlorobenzene. The yield is improved by 2.4 percent compared with benzene which is not subjected to anhydrous treatment. The molar ratio of anhydrous benzene to chlorine is 1.8: 1.3, the iron catalyst accounts for 1 percent of the total weight of the anhydrous benzene and the chlorine.
Example 5
An environment-friendly chlorobenzene production process comprises the following steps:
step one, mixing the adsorbing material prepared in the embodiment 3 with industrial pure benzene, mixing for 11 hours at the temperature of 30 ℃, and then filtering under the condition of a magnetic field to obtain anhydrous benzene for later use;
and secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 85 ℃, reacting for 1.2h, washing the obtained reaction solution at 25 ℃ after the reaction is finished, neutralizing the washed solution with 25 mass percent of ammonia water, extracting with anhydrous benzene, and concentrating the organic phase under reduced pressure to obtain the chlorobenzene. The yield is improved by 2.5 percent compared with benzene which is not subjected to anhydrous treatment.
Example 6
An environment-friendly chlorobenzene production process comprises the following steps:
step one, mixing the adsorbing material prepared in the embodiment 3 with industrial pure benzene, mixing for 12 hours at the temperature of 30 ℃, and then filtering under the condition of a magnetic field to obtain anhydrous benzene for later use;
and secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 90 ℃, reacting for 1.5 hours, after the reaction is finished, washing the obtained reaction solution at the temperature of 30 ℃, neutralizing the washed solution with ammonia water with the mass fraction of 30%, extracting with anhydrous benzene, and concentrating the organic phase under reduced pressure to obtain the chlorobenzene. The yield is improved by 2.5 percent compared with benzene which is not subjected to anhydrous treatment.
The adsorbing materials used in examples 4 to 6 were recovered, dried at 350 ℃ for 4 hours, and reused without decreasing the water absorption rate, and it can be seen that the adsorbing materials prepared by the present invention have good regeneration effect.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The production process of the environment-friendly chlorobenzene is characterized by comprising the following steps of:
firstly, mixing an adsorption material and industrial pure benzene, mixing for 10-12h at the temperature of 30 ℃, and then filtering to obtain anhydrous benzene for later use;
and secondly, mixing chlorine, anhydrous benzene and an iron catalyst in a reactor, setting the temperature to be 80-90 ℃, reacting for 1-1.5h, washing the obtained reaction liquid after the reaction is finished, neutralizing the washed solution with ammonia water, extracting and concentrating to obtain the chlorobenzene.
2. The production process of the environmental-friendly chlorinated benzene as claimed in claim 1, wherein the adsorbing material is prepared by the following steps:
dropping a sodium carbonate solution into acrylic acid until the neutralization degree is 80%, then adding acrylamide, potassium persulfate and a cross-linking agent, stirring for 5min after the addition is finished, adding an additive, uniformly mixing, freezing for 12h at the temperature of-10 ℃, taking out after freezing, adding span-80 and cyclohexane, stirring for 1h at the temperature of 45 ℃, then heating to 70 ℃, stirring for 4h, filtering after the reaction is finished, washing, drying to constant weight in vacuum at the temperature of 80 ℃ after the washing is finished, crushing, sieving by a 20-mesh sieve, and activating for 3-4h at the temperature of 350 ℃ to obtain the adsorbing material.
3. The production process of the environmental-friendly chlorobenzene according to claim 2, wherein the mass fraction of the sodium carbonate solution is 13%, and the mass ratio of the acrylic acid, the acrylamide, the potassium persulfate, the crosslinking agent and the additive is 100: 30: 0.2: 0.04: 7-8; the mass ratio of the acrylic acid to the span-80 to the cyclohexane is 1: 0.02: 1; the cross-linking agent is one of N, N-methylene bisacrylamide and diethylenetriamine.
4. The process for producing environmentally friendly chlorinated benzenes according to claim 2, wherein the additive is prepared by the steps of:
mixing chitosan and acetic acid solution, adding magnetic ferroferric oxide, stirring for 1h, adding 4,4' -dicyclohexylmethane diisocyanate and stannous octoate, stirring for 2h, filtering, washing, filtering and drying to obtain magnetic particles, mixing MCM-41 and dimethyl sulfoxide, adding magnetic particles, adding stannous octoate, stirring for 2h at 25 ℃, filtering after the reaction is finished, washing with absolute ethyl alcohol, and freeze-drying to obtain the additive after the washing is finished.
5. The production process of environmental chlorobenzene according to claim 4, wherein the mass fraction of the acetic acid solution is 2%, and the amount ratio of the chitosan to the acetic acid solution is 0.2 g: 50 mL; the dosage ratio of the chitosan, the magnetic ferroferric oxide, the 4,4' -dicyclohexylmethane diisocyanate and the stannous octoate is 0.2 g: 0.1 g: 0.2 mL: 0.06 g; the use ratio of MCM-41, dimethyl sulfoxide, magnetic particles and stannous octoate is 0.2 g: 50mL of: 0.2 g: 0.06 g.
6. The production process of the environmental-friendly chlorobenzene according to claim 1, wherein the mass fraction of the ammonia water used for neutralization is 20-30%.
7. The production process of the environmental-friendly chlorobenzene according to claim 1, wherein the temperature is set to be 20-30 ℃ during the washing.
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| CN106565415A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing monochlorobenzene |
| CN109053361A (en) * | 2018-09-11 | 2018-12-21 | 安徽东至广信农化有限公司 | For reducing the method for impurity dichloro-benzenes in benzene chloride production technique |
| CN109096042A (en) * | 2018-09-11 | 2018-12-28 | 安徽东至广信农化有限公司 | A kind of novel production process of Benzene Chloride |
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| CN106565415A (en) * | 2015-10-12 | 2017-04-19 | 中国石油化工股份有限公司 | Method for preparing monochlorobenzene |
| CN109053361A (en) * | 2018-09-11 | 2018-12-21 | 安徽东至广信农化有限公司 | For reducing the method for impurity dichloro-benzenes in benzene chloride production technique |
| CN109096042A (en) * | 2018-09-11 | 2018-12-28 | 安徽东至广信农化有限公司 | A kind of novel production process of Benzene Chloride |
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