CN113651674A - System and method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid - Google Patents
System and method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid Download PDFInfo
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- CN113651674A CN113651674A CN202010399202.3A CN202010399202A CN113651674A CN 113651674 A CN113651674 A CN 113651674A CN 202010399202 A CN202010399202 A CN 202010399202A CN 113651674 A CN113651674 A CN 113651674A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 222
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000007788 liquid Substances 0.000 title claims abstract description 100
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052921 ammonium sulfate Inorganic materials 0.000 title claims abstract description 95
- 235000011130 ammonium sulphate Nutrition 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 88
- 238000004821 distillation Methods 0.000 title claims abstract description 58
- 238000001704 evaporation Methods 0.000 claims abstract description 93
- 230000008020 evaporation Effects 0.000 claims abstract description 82
- 239000000706 filtrate Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 18
- 239000002699 waste material Substances 0.000 claims abstract description 14
- 239000012808 vapor phase Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims description 41
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 33
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000007670 refining Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000002245 particle Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005303 weighing Methods 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000004042 decolorization Methods 0.000 description 7
- 238000003828 vacuum filtration Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- JZMJDSHXVKJFKW-UHFFFAOYSA-N methyl sulfate Chemical compound COS(O)(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-N 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- -1 and preferably Chemical compound 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a system and a method for preparing ammonium sulfate and methanol by using dimethyl sulfate evaporation kettle residual liquid, wherein the system comprises a neutralization reaction unit, a separation unit and a post-treatment unit; the neutralization reaction unit comprises a neutralization kettle, feed inlets of the neutralization kettle comprise a residual liquid feed inlet and a neutralizing agent feed inlet, and the residual liquid feed inlet is connected with a residual liquid outlet of the dimethyl sulfate distillation kettle; the separation unit comprises a filter press, a feed inlet of the filter press is connected with a discharge outlet of the neutralization kettle, and an outlet of the filter press comprises a filtrate outlet and a filter residue outlet; the post-treatment unit comprises an evaporation kettle and a rectifying tower, a feed inlet of the evaporation kettle is connected with a filtrate outlet of the filter press, a discharge outlet of the evaporation kettle comprises a vapor-phase discharge outlet and a material outlet, the vapor-phase discharge outlet is communicated with a feed inlet of the rectifying tower, and the material outlet obtains ammonium sulfate; the top of the rectifying tower is provided with a solvent outlet, and the bottom of the rectifying tower is provided with a waste liquid outlet. The system can recover ammonium sulfate and methanol, and has reasonable scheme and no environmental pollution.
Description
Technical Field
The invention relates to the technical field of chemical waste liquid treatment, in particular to a system and a method for preparing ammonium sulfate and methanol from dimethyl sulfate evaporation kettle residual liquid.
Background
The synthetic method of the dimethyl sulfate comprises a sodium salt method, a direct reaction method of anhydrous sulfuric acid and methanol, a synthesis method of dimethyl ether and sulfur trioxide, a synthesis method of chlorosulfonic acid, a methyl hydrogen sulfate method and the like, wherein except the synthesis method of the dimethyl ether and the sulfur trioxide, other methods have the problems of low product yield, large raw material consumption and serious equipment corrosion. Industrially, the process of the synthesis of dimethyl ether and sulfur trioxide is: and (2) dehydrating methanol to obtain dimethyl ether, carrying out chemical reaction with sulfur trioxide in a reaction kettle to generate a dimethyl sulfate crude product, feeding the dimethyl sulfate crude product into a distillation kettle, distilling the dimethyl sulfate at the temperature of 110-140 ℃ under the vacuum degree of 94.7KPa, condensing, collecting in a refined ester storage tank, and carrying out subsequent treatment on the residual liquid in the distillation kettle. When the sulfur trioxide reacts with the dimethyl ether, not only the dimethyl sulfate is generated, but also a plurality of other byproducts are generated. After the dimethyl sulfate is separated from the mixed system, methyl bisulfate, methanol, residual carbon, a small amount of incompletely decomposed dimethyl sulfate and the like exist, and if the dimethyl sulfate is directly discharged, the environment is seriously polluted. At present, three methods for treating dimethyl sulfate residual liquid in China are mainly used, namely, dimethyl sulfate residues are hydrolyzed and then neutralized by sodium hydroxide; the second method is to recover sulfuric acid from the raffinate using an ion exchange resin. Thirdly, lime or ammonia water is adopted for neutralization.
Disclosure of Invention
The present inventors have considered that the above treatment method has the following problems: (1) the alkali neutralization method needs to consume more liquid alkali, and although the byproduct sodium sulfate can be recovered, the market capacity is limited, and the production cost is higher. (2) Hydrolyzing the residual liquid and recovering sulfuric acid by an ion exchange resin method. The process can obtain a certain amount of sulfuric acid, but the cost of the recovered sulfuric acid is high, and the operating environment is severe. Since the enterprises producing dimethyl sulfate can usually produce sulfuric acid by themselves, it is not cost-effective from the economic viewpoint. (3) Lime neutralization produces more calcium sulfate that is not available. There are few enterprises that adopt. In the existing reports, although enterprises also adopt an ammonia water neutralization method to treat the residual liquid, the residual liquid is a dark brown complex mixed system containing multiple components, pure ammonium sulfate cannot be obtained by directly adding ammonia water, and the obtained black mixed solution containing ammonium sulfate (also comprising water, methanol and amine substances) cannot be sold to the outside, contains a large amount of black organic matter impurities, is difficult to treat, contains high nitrogen content in the waste liquid and has high treatment cost, so that the obtained ammonium sulfate has low purity, can only be completely discharged after the waste liquid is neutralized, and causes serious resource waste.
The technical problem solved by the invention is as follows: the dimethyl sulfate residual liquid has high toxicity, strong acidity and many impurities. The existing treatment technology has high cost and great environmental pollution, and can not extract useful chemical products, and chemical components with recovery value in residual liquid are not utilized, thereby causing resource waste.
The purpose of the invention is: the problem of discharging the residual liquid in the dimethyl sulfate production is solved, the method for preparing the high-purity ammonium sulfate crystal from the residual liquid in the dimethyl sulfate production is provided, and meanwhile, part of organic solvents such as methanol and the like can be recycled, so that the production waste liquid which is difficult to treat is subjected to harmless treatment.
In order to solve the technical problem, the invention adds ammonia water to neutralize the residual liquid in the production of dimethyl sulfate, and the solution is decolorized, separated from solid and liquid and evaporated to obtain ammonium sulfate after reaction. The coarse product is recrystallized for the second time to obtain the high-purity large-particle ammonium sulfate finished product. The invention solves the problem of environmental pollution caused by the waste liquid from dimethyl sulfate production, and has the advantages of less equipment investment, simple process, mild operation condition, no environmental pollution, safety and environmental protection.
Specifically, aiming at the defects of the prior art, the invention provides the following technical scheme:
a system for preparing ammonium sulfate and methanol by using dimethyl sulfate distillation kettle residual liquid is characterized by comprising a neutralization reaction unit, a separation unit and a post-treatment unit;
the neutralization reaction unit comprises a neutralization kettle, the feed inlets of the neutralization kettle comprise a raffinate feed inlet and a neutralizing agent feed inlet, and the raffinate feed inlet is connected with a raffinate outlet of the dimethyl sulfate distillation kettle;
the separation unit comprises a filter press, a feed inlet of the filter press is connected with a discharge outlet of the neutralization kettle, and an outlet of the filter press comprises a filtrate outlet and a filter residue outlet;
the post-treatment unit comprises an evaporation kettle and a rectifying tower, a feed inlet of the evaporation kettle is connected with a filtrate outlet of the filter press, a discharge outlet of the evaporation kettle comprises a vapor-phase discharge outlet and a material outlet, the vapor-phase discharge outlet is communicated with a feed inlet of the rectifying tower, and the material outlet obtains ammonium sulfate; the top of the rectifying tower is provided with a solvent outlet, and the bottom of the rectifying tower is provided with a waste liquid outlet;
the material added into the neutralizing agent feed port comprises ammonia water, and preferably, the material added into the neutralizing agent feed port also comprises a flocculating agent.
Preferably, the flocculant is selected from sodium polyacrylate or polyacrylamide.
Preferably, the neutralization tank is lined with an enamel material.
Preferably, the above-mentioned system for preparing ammonium sulfate and methanol with dimethyl sulfate distillation still raffinate, wherein, be provided with the decoloration tower between pressure filter and the evaporation kettle, the feed inlet of decoloration tower is connected with the filtrating export of pressure filter, the discharge gate of decoloration tower is connected with the feed inlet of evaporation kettle.
Preferably, in the above system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, a filtering device is arranged between the decoloring tower and the evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the decoloring tower, and a filtrate outlet of the filtering device is connected with a feed inlet of the evaporation kettle.
Preferably, in the above system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the filtering device is a precision filter. The precision filter can separate particles with the particle size of 5-20 mu m.
Preferably, in the above-mentioned system for preparing ammonium sulfate and methyl alcohol with dimethyl sulfate distillation kettle raffinate, the system still includes refined unit, refined unit is including dissolving cauldron and second reation kettle, the feed inlet of dissolving cauldron with the material exit linkage of the reation kettle of aftertreatment unit, the discharge gate of dissolving cauldron with the feed inlet of second reation kettle is connected, the material export of second reation kettle obtains the ammonium sulfate.
Preferably, in the above-mentioned system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still raffinate, be provided with filter equipment between the dissolving kettle and the second evaporating kettle, filter equipment's feed inlet is connected with the discharge gate of dissolving kettle, filter equipment's filtrate export with the feed inlet of second evaporating kettle is connected.
Preferably, in the above system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the filtering device is a precision filter.
The invention also provides a method for preparing ammonium sulfate and methanol by using the residual liquid of the dimethyl sulfate distillation kettle, which is characterized by comprising the following steps:
opening the system for preparing ammonium sulfate and methanol by using the dimethyl sulfate distillation kettle residual liquid, introducing the dimethyl sulfate distillation kettle residual liquid into the neutralization kettle, adding a neutralizing agent into a neutralizing agent feeding port until the mixed system is neutral, introducing a material obtained after the reaction into a filter press, introducing the obtained filtrate into an evaporation kettle, evaporating to remove a liquid phase, precipitating ammonium sulfate crystals, introducing a vapor phase substance obtained from the evaporation kettle into a rectifying tower, separating, and then obtaining an organic solvent from the top of the rectifying tower and obtaining a waste liquid from the bottom; preferably, a flocculating agent is also added into the neutralizing agent feed inlet.
Preferably, in the method for preparing ammonium sulfate and methanol from the dimethyl sulfate distillation kettle residual liquid, a decoloring tower is arranged between the filter press and the evaporation kettle, a feed inlet of the decoloring tower is connected with a filtrate outlet of the filter press, and a discharge outlet of the decoloring tower is connected with a feed inlet of the evaporation kettle;
wherein, the filtrate of the filter press is introduced into a decoloring tower, and the filtrate is decolored and then introduced into an evaporation kettle.
Preferably, in the method for preparing ammonium sulfate and methanol from the dimethyl sulfate distillation kettle residual liquid, a filtering device is arranged between the decoloring tower and the evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the decoloring tower, and a filtrate outlet of the filtering device is connected with a feed inlet of the evaporation kettle;
wherein, the filtrate of the filter press is decolorized and then is introduced into a filtering device, and the filtrate obtained by the filtering device is introduced into an evaporation kettle.
Preferably, in the method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid, the system further comprises a refining unit, the refining unit comprises a dissolving kettle and a second evaporation kettle, a feed inlet of the dissolving kettle is connected with a material outlet of the evaporation kettle of the post-treatment unit, a discharge outlet of the dissolving kettle is connected with a feed inlet of the second evaporation kettle, and a material outlet of the second evaporation kettle obtains ammonium sulfate;
and (3) introducing crude ammonium sulfate obtained from a material outlet of an evaporation kettle of the post-treatment unit into a dissolving kettle, adding a hydrosolvent, introducing the obtained material into a second evaporation kettle, and separating out refined ammonium sulfate crystals after evaporating a liquid phase.
Preferably, in the method for preparing ammonium sulfate and methanol from the dimethyl sulfate distillation kettle residual liquid, a filtering device is arranged between the dissolving kettle and the second evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the dissolving kettle, and a filtrate outlet of the filtering device is connected with a feed inlet of the second evaporation kettle;
and introducing the materials obtained in the dissolving kettle into a filtering device, and introducing the obtained filtrate into a second evaporation kettle.
Preferably, in the above method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the reaction temperature in the neutralization still is 10-90 ℃.
Preferably, in the method for preparing ammonium sulfate and methanol by using the dimethyl sulfate distillation still residual liquid, the neutralizing agent is used for adjusting the material to be neutral and then reacting for 10-30 min.
Preferably, in the above method for producing ammonium sulfate and methanol from dimethyl sulfate distillation still residue, the feeding rate of the neutralizing agent is 2.0 to 2.3kg/h, preferably 2.2 to 2.3kg/h, more preferably 2.25 kg/h.
Preferably, the concentration of the ammonia water is 20-25 wt%, and the addition amount of the flocculating agent accounts for 0.05-1 wt% of the mass of the dimethyl sulfate residual liquid.
Preferably, in the method for preparing ammonium sulfate and methanol by using the dimethyl sulfate distillation kettle residual liquid, the decolorizing agent is activated carbon, the particle size is 1-4mm, the iodine value is 500-900mg/g, and the bulk density is 0.4-0.5g/cm3Preferably 0.45 to 0.55g/cm3。
Preferably, in the above method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the temperature of the evaporation still of the post-treatment unit is 100-105 ℃.
Preferably, in the method for preparing ammonium sulfate and methanol by using the dimethyl sulfate distillation kettle residual liquid, the heating time of the evaporation kettle is 30-45min, preferably 35-40 min.
Preferably, in the above method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the temperature of the dissolution still is 70-90 ℃.
Preferably, in the above method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residue, the temperature of the second evaporation still of the refining unit is 100-105 ℃.
Preferably, in the method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid, the parameters of the rectification process of the rectification tower are as follows: the top temperature of the rectifying tower is 64-67 ℃, the bottom temperature of the rectifying tower is 104-105 ℃, the reflux ratio is 1.0-2.0, preferably 1.5-2, and the top pressure: 101.3-103 KPa; kettle pressure: 105KPa 115 KPa; number of trays: 5 to 10, preferably 6 to 10; a wire mesh packing is adopted.
Preferably, in the method for preparing the ammonium sulfate and the methanol by using the dimethyl sulfate distillation kettle residual liquid, the treatment capacity of the rectifying tower is 50-100L/h; the height of the rectifying tower is 4-6 m, and the inner diameter of the tower is 80-100 mm.
The invention has the advantages that: the method has the advantages of reasonable and feasible scheme, simple process route, no environmental pollution and thorough treatment, and the color, the granularity and the product purity of the ammonium sulfate all accord with the national standard. The product has better market prospect, not only can be used as a fertilizer, but also can be used in the aspects of textile, leather, medicine and the like, and compared with the sodium sulfate prepared by an alkali neutralization method, the product ammonium sulfate has better market prospect. In addition, the recovered methanol is an important basic organic chemical raw material, is widely applied to various industries of national economy, is used for manufacturing formaldehyde, pesticides and the like, and is commonly used as an extractant of organic matters, a denaturant of alcohol and the like; the liquid phase is treated by the technology to obtain useful chemical new products such as high-purity ammonium sulfate, methanol and the like, and basically no new three wastes are generated. The black solid residue separated from the mixed system can be used as fuel, and the treated residual liquid has no biochemical toxicity and no suspended matter and can be directly discharged.
Drawings
FIG. 1 is a process diagram of a system for producing ammonium sulfate and methanol from dimethyl sulfate still bottoms as described in example 1.1.
FIG. 2 is a process diagram of a system for producing ammonium sulfate and methanol from dimethyl sulfate still bottoms as described in example 1.3.
Detailed Description
In view of the problems that the existing treatment method of the dimethyl sulfate residual liquid has higher cost and valuable components in the residual liquid are not reasonably utilized, the invention provides a treatment method of the residual liquid in the dimethyl sulfate production (namely, the residual liquid in a dimethyl sulfate distillation kettle), belonging to the technical field of the treatment of three wastes in chemical industry.
In a preferred embodiment, the invention provides a system and a method for preparing ammonium sulfate and methanol by using dimethyl sulfate distillation still residual liquid, wherein the production residual liquid or the distillation still residual liquid of the dimethyl sulfate is the kettle bottom residual liquid after the reaction of sulfur trioxide and dimethyl ether and the dimethyl sulfate is removed, and the system is a dark black solid-liquid mixed system containing residual carbon, methanol, methyl hydrogen sulfate and a small amount of dimethyl sulfate.
In the treatment process of the dimethyl sulfate residual liquid, the process is characterized in that: the production residual liquid of the dimethyl sulfate is firstly neutralized by ammonia water with the mass fraction of 15-25%, and a mixed system after reaction is filtered by a filter press. Drying the filter cake and then using the dried filter cake as solid fuel; the filtrate was decolorized with powdered activated carbon for 24 hours and then filtered. The filtrate is evaporated in a drying kettle to remove water to obtain crude ammonium sulfate crystals.
Preferably, in the method for treating the dimethyl sulfate residual liquid, the process is characterized in that a liquid product distilled from a distillation kettle is condensed and cooled and then is separated by a rectifying tower, methanol is obtained at the tower top, and the tower kettle component is water and can be used as process water. Dissolving the coarse ammonium sulfate crystal again by using the kettle liquid of the rectifying tower, filtering impurities by using a precision filter, slowly evaporating 95% of water, and separating the liquid phase by using a centrifugal machine to obtain pure large-particle ammonium sulfate crystal. The centrifuged mother liquor is returned to the mother liquor tank.
Preferably, in the method for treating the dimethyl sulfate residual liquid, the method comprises the following steps: the filtrate collected for the first time needs to be decolorized by active carbon. The activated carbon is granular activated carbon.
Preferably, in the method for treating the dimethyl sulfate residual liquid, the method comprises the following steps: the ammonium sulfate crystal separated out by the first crystallization needs to be dissolved again, filtered precisely and evaporated, thereby obtaining large-particle crystals (1-4 mm).
Preferably, in the process for treating the dimethyl sulfate residual liquid, the following steps are included: the outlet of the dimethyl sulfate distillation kettle is connected with the inlet of the neutralization kettle. The outlet of the neutralization kettle is connected with the inlet of the filter press. The liquid outlet of the filter press is connected with a decoloring kettle. The decoloring kettle is connected with an inlet of the precision filter. The liquid outlet of the precision filter is connected with the inlet of the evaporation kettle. The liquid outlet of the evaporation kettle is connected with the inlet of the rectifying tower. The outlet of the solid-liquid mixing system is connected with a centrifuge. The liquid outlet of the centrifuge is connected with the mother liquid tank. And a solid outlet obtains ammonium sulfate crystals.
Preferably, in the method for treating the dimethyl sulfate residual liquid, the ammonium sulfate crystal obtained from the solid outlet of the centrifuge is secondarily dissolved by the liquid in the tower bottom of the rectifying tower. After filtration again, the water content of the solution was slowly evaporated. Large-particle and high-purity ammonium sulfate crystals can be obtained.
In another preferred embodiment, the method for treating the residual liquid in the production of dimethyl sulfate comprises the steps of slowly dropwise adding ammonia water with the concentration of 20-25% and a sodium polyacrylate solution with the concentration of 0.05-1% into the residual liquid in the production of dimethyl sulfate under the condition of controlling the reaction temperature, wherein the adding amount of the ammonia water is determined by the pH value of a mixed system, and the dropwise adding of the ammonia water is stopped when the pH value of the reaction system is equal to 7. The reaction temperature is controlled at 10-90 ℃. And after the dropwise addition is finished, continuously reacting for 20-30 min. Adding powdered activated carbon into the obtained black-brown mixed system for decoloring for 12-48 h.
Preferably, in the above method, the solid-liquid phase is separated by a filter press. And (3) evaporating 95% of liquid phase of the filtrate in an evaporation kettle, wherein the main component of the precipitated crystal is ammonium sulfate, the mass fraction of the precipitated crystal is 85-95%, steam from the evaporation kettle is condensed and cooled by a heat exchanger, and the collected liquid product is used for recovering methanol in the liquid product by a rectifying tower. The water can be recycled or discharged.
Preferably, in the above method, the purified product is obtained in a purity of not less than 99% in large particles. Adding the obtained crude ammonium sulfate into purified water until the crude ammonium sulfate is completely dissolved, wherein the dissolving temperature is 70-90 ℃. And removing impurities in the solution by using a precision filter. And evaporating 95% of water in the filtrate by using an evaporator again, and separating a liquid phase by using a centrifugal machine to obtain high-purity ammonium sulfate (the nitrogen content is more than or equal to 21%) with the mass fraction of not less than 99%. The liquid is sent to a mother liquid tank for recovery.
The quality index of the ammonium sulfate finished product obtained by the method meets the quality requirement of GB535-1995 high-class products.
The method can obtain the byproduct methanol while obtaining the ammonium sulfate. The production process can not generate new environmental pollution, and is safe and environment-friendly.
The system and method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residue according to the present invention are further illustrated by the following specific examples
In the following examples, information on the reagents and instruments used is shown in the following table:
TABLE 1 information Table of reagents used in examples
Example 1 System for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid
Example 1.1
The system for preparing ammonium sulfate and methanol by using dimethyl sulfate distillation kettle residual liquid comprises:
(1) neutralization reaction unit
The neutralization reaction unit comprises a neutralization kettle, feed inlets of the neutralization kettle comprise a dimethyl sulfate residual liquid feed inlet and a neutralizing agent feed inlet, and the dimethyl sulfate residual liquid feed inlet is connected with a dimethyl sulfate distillation kettle residual liquid outlet.
The lining enamel material of the neutralization kettle is a composite material which is formed by firmly combining metal and inorganic oxide and is formed by firing one or more layers of vitreous glazes coated on the surface of the metal at high temperature. The main components are as follows: SiO 22(40-45％)，Al2O3(2-7％)，B2O3(10-15%), alkali metal oxide (5-20%, Na)2O，Li2O，K2O), other oxides (5-10%, PbO, TiO)2，Cao，F2)。
(2) Separation unit
The separation unit comprises a filter press, a feed inlet of the filter press is connected with a discharge outlet of the neutralization kettle, and an outlet comprises a filtrate outlet and a filter residue outlet.
(3) Post-processing unit
The post-treatment unit comprises a decoloring tower, an evaporation kettle and a rectifying tower, wherein a feed inlet of the decoloring tower is connected with a filtrate outlet of a filter press, an outlet of the decoloring tower is connected with the feed inlet of the evaporation kettle, an outlet of the evaporation kettle comprises a material outlet and a vapor phase outlet, the vapor phase outlet is communicated with the feed inlet of the rectifying tower, a solvent outlet is arranged at the top of the rectifying tower, a waste water outlet is arranged at the bottom of the rectifying tower, a solvent groove is connected to the solvent outlet, and a waste water groove is connected to the waste water outlet. Wherein, the evaporation kettle is a device with distillation function and condensation function.
The process diagram of the system described in this embodiment is as shown in fig. 1, in the using process, the residual liquid of the dimethyl sulfate distillation kettle is introduced into the neutralization kettle, a neutralizing agent is added, the materials are adjusted to be neutral, the reaction is carried out at 10-90 ℃, the obtained materials are introduced into the filter press, the obtained filter residue is recycled as solid fuel, the obtained filtrate is introduced into the decoloring tower, after being treated by the decoloring agent, the obtained materials are introduced into the evaporation kettle, 95% of liquid phase is evaporated, the main component of the precipitated crystal is ammonium sulfate, the vapor phase substance evaporated from the evaporation kettle is condensed to obtain condensate, the condensate is introduced into the rectification tower, the organic solvents such as methanol and methylamine are obtained from the solvent outlet after separation, and the wastewater is obtained from the wastewater outlet.
Example 1.2
The system for preparing ammonium sulfate and methanol from dimethyl sulfate still bottoms described in this example is similar to example 1.1 with the following differences: a filtering device, preferably a precision filter (capable of separating particles with the particle size of 5-20 μm) is connected between the decoloring tower and the evaporation kettle, and a filtrate outlet of the filtering device is connected with a feed inlet of the evaporation kettle.
Example 1.3
The system for preparing ammonium sulfate and methanol from dimethyl sulfate still bottoms described in this example is similar to example 1.1 with the following differences: the system also comprises a refining unit, wherein the refining unit comprises a dissolving kettle, a filtering device, a second evaporating kettle and a centrifugal machine. The feed inlet of the dissolving kettle is connected with the evaporation kettle material outlet of the post-processing unit, the discharge outlet is connected with the filtering device, the filtrate outlet of the filtering device is connected with the second evaporation kettle, and the material outlet of the second evaporation kettle is connected with the centrifugal machine. Wherein the filtering device is preferably a precision filter.
The process diagram of the system of this embodiment is as shown in fig. 2, and in the using process, the crude ammonium sulfate obtained from the evaporation kettle of the post-treatment unit is added into the dissolution kettle, the solution is added with water and is completely dissolved, and then the solution is introduced into the filtering device, the filtrate obtained from the filtering device is introduced into the second evaporation kettle, after 95% of water is evaporated, the liquid phase is separated by the centrifuge, and the refined ammonium sulfate is obtained.
In examples 1.1 to 1.3, the neutralizing agent comprises ammonia water, and preferably, sodium polyacrylate. The decolorizing agent is selected from granular or powdered activated carbon, and the specific surface area is 500-900 mg/g. The temperature of the evaporation kettle of the post-treatment unit is 100-105 ℃.
The parameters of the rectification process are as follows: the tower top temperature of the rectifying tower is 64-67 ℃, the tower bottom temperature is 104-: 101.3-103 KPa; kettle pressure: 105KPa 115 KPa; number of trays: 5 to 10, preferably 6 to 10; a wire mesh packing is adopted. Treatment capacity: 50-100L/h; the height of the tower is 4-6 m, and the inner diameter of the tower is 80-100 mm.
The temperature of the dissolving kettle is 70-90 ℃, and the temperature of the evaporation kettle of the refining unit is 100-105 ℃.
EXAMPLE 2 method for preparing ammonium sulfate from dimethyl sulfate distillation still residual liquid
Example 2.1
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly adding dropwise (dropwise adding speed: 2.25kg/h) 20% ammonia water at 10 deg.C, stopping adding when the pH value of the system reaches 7, adding 745g ammonia water, and continuing to react for 20 min. Vacuum filtration was carried out, and the residue was dried and weighed to give a mass of 10.21 g. Activated carbon (bulk density 0.45 g/cm) was used for the filtrate3) Decoloring for 48 hours, performing suction filtration again to obtain 1210.2g of filtrate, transferring the filtrate into a 2L flask, heating at 100 ℃ for 40min, condensing steam, weighing, feeding the condensate with the mass of 665g into a rectifying tower, and rectifying to obtain 110g of methanol (boiling range: 64.7-66 ℃), and the white crystal ammonium sulfate 505g is obtained after the steam condensation, and the purity: 89.94%, particle size of 1-2mm, nitrogen content: 20.17 percent.
Wherein the bulk density of the activated carbon in the decolorization process is 0.45g/cm3。
Wherein the parameters of the rectifying tower are as follows: the top temperature is 64 ℃, the bottom temperature is 104 ℃, the reflux ratio is 1.5, the top pressure is 101.3KPa, the bottom pressure is 105KPa, the number of tower plates is 6, a wire mesh packing is adopted, the treatment capacity is 50L/h, the height of the tower is 4m, and the inner diameter of the tower is 80 mm.
Among them, the identification method of methanol is GB338-2004, and the detection method of ammonium sulfate and nitrogen content thereof is GB 535-1995.
Example 2.2
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Aqueous ammonia having a concentration of 20% was slowly added dropwise (dropping speed: 2.25kg/h) at 30 ℃ until the pH of the system reached 7, at which time the amount of aqueous ammonia was 750 g. The reaction was continued for 30 min. Weighing, vacuum filtering, drying the filter residue and weighing to obtain 10.13g of filter residue. Decolorizing the filtrate for 48h by using activated carbon, performing suction filtration again to obtain 1217g of filtrate, transferring the filtrate into a 2L flask, heating at 100 ℃ for 38min, condensing the steam, weighing, feeding 674g of condensate into a rectifying tower, rectifying to obtain 119g of methanol (boiling range: 64.7-66 ℃), condensing the steam to obtain 503g of white crystals, and obtaining the purity: 90.43%, particle size of 1-2mm, nitrogen content: 20.12 percent.
Wherein the bulk density of the activated carbon in the decolorization process is 0.55g/cm3。
Wherein the parameters of the rectifying tower are as follows: the tower top temperature is 67 ℃, the tower kettle temperature is 105 ℃, the reflux ratio is 2, the top pressure is 103KPa, the kettle pressure is 115KPa, the tower plate number is 10, a wire mesh packing is adopted, the treatment capacity is 100L/h, the tower height is 6 m, and the tower inner diameter is 100 mm.
Example 2.3
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly adding ammonia water with the concentration of 20% (the adding speed is 2.25kg/h) dropwise at the temperature of 50 ℃, stopping adding ammonia water when the pH value of the system reaches 7, adding 752g of ammonia water, adding 0.05% of sodium polyacrylate (accounting for the mass fraction of the dimethyl sulfate residual liquid), and continuing to react for 30 min. Vacuum filtration was carried out, and the mass of the residue was 11.19g after drying. Decolorizing the filtrate for 48h with activated carbon, performing suction filtration again to obtain 1350.2g of filtrate, transferring into a 2L flask, heating at 100 ℃ for 35min, condensing steam, weighing, feeding into a rectifying tower, rectifying to obtain 117g of methanol (boiling range: 64.7-66 ℃) after rectification, and condensing steam to obtain 512g of white crystals with purity: 90.28%, particle size of 1-2mm, nitrogen content: 20.22 percent.
Wherein the parameters of the rectifying tower are as follows: the tower top temperature is 65 ℃, the tower kettle temperature is 104 ℃, the reflux ratio is 1.8, the top pressure is 102KPa, the kettle pressure is 110KPa, the tower plate number is 8, a wire mesh packing is adopted, the treatment capacity is 80L/h, the tower height is 5m, and the tower inner diameter is 90 mm.
Example 2.4
Using the system described in example 1.3, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Aqueous ammonia having a concentration of 25% was slowly added dropwise (dropping speed: 2.0kg/h) at 10 ℃ until the pH of the system reached 7, and the addition of aqueous ammonia was 596 g. The reaction was continued for 20 min. Vacuum filtration was carried out, and the residue was dried and weighed to give a mass of 10.29 g. Decolorizing the filtrate for 24h by using activated carbon, performing suction filtration again to obtain 1090g of filtrate, transferring the filtrate into a 2L flask, heating at the temperature of 100 ℃ for 45min, condensing steam, weighing, wherein the mass of a condensate is 539g, rectifying to obtain 117g of methanol (the boiling range is 64.7-66 ℃), condensing the steam to obtain 508g of white crystals, and obtaining the purity: 90.1%, particle size of 1-2mm, nitrogen content: 20.23 percent. Wherein, the decolorization process and the rectification process are the same as in example 2.1.
And (3) refining: the obtained white crystals were dissolved twice in 500ml of distilled water at 90 ℃ and filtered through precision filter paper (pore size 1-3 μm), and water was slowly distilled off at 100 ℃ to obtain 496g of crystals with purity: 99.4%, particle size of 1-4mm, nitrogen content: 21.05 percent
Example 2.5
Using the system described in example 1.3, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly adding dropwise (dropwise adding speed: 2.30kg/h) 25% ammonia water at 10 deg.C, stopping adding ammonia water when pH value of the system reaches 7, at this time adding 594g ammonia water, and continuing reaction for 30 min. Vacuum filtration was carried out, and the mass of the residue was 10.27g after drying. Decolorizing the filtrate for 48h with activated carbon, performing suction filtration again to obtain 1089g of filtrate, transferring into a 2L flask, heating at 100 ℃ for 35min, condensing the steam, weighing, wherein the mass of the condensate is 533g, rectifying to obtain 116g of methanol (the boiling range is 64.7-66 ℃), condensing the steam to obtain 507g of white crystals, and obtaining the purity: 90.9%, particle size of 1-2mm, nitrogen content: 20.29 percent. Wherein, the decolorization process and the rectification process are the same as in example 2.1.
And (3) refining: and (3) adding 500ml of distilled water into the obtained white crystals for secondary dissolution, wherein the dissolution temperature is 70 ℃, filtering by using precision filter paper, and slowly evaporating water at 100 ℃ to obtain 494g of crystals with the purity: 99.20%, the grain diameter is 1-4mm, and the nitrogen content is as follows: 21.03 percent
Example 2.6
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly dropwise adding (dropwise adding speed: 2.25kg/h) 25% ammonia water at 10 ℃, stopping dropwise adding when the pH value of the system reaches 7, adding 594g of ammonia water, adding 1.0% sodium polyacrylate (accounting for the mass fraction of the dimethyl sulfate residual liquid), and continuing to react for 30 min. Using precision filter paper, carrying out vacuum filtration, drying filter residues, and weighing to obtain the product with the mass of 11.18 g. Decolorizing the filtrate for 48h with activated carbon, performing suction filtration again to obtain 1089g of filtrate, transferring into a 2L flask, heating at 100 ℃ for 40min, condensing the steam, weighing, wherein the mass of the condensate is 527g, rectifying to obtain 119g of methanol (boiling range: 64.7-66 ℃), condensing the steam to obtain 515g of white crystals, and obtaining the purity: 90.9%, particle size of 1-2mm, nitrogen content: 20.45 percent. Wherein, the decolorization process and the rectification process are the same as in example 2.1.
And (3) refining: after the obtained white crystals were dissolved twice in 500ml of distilled water at a dissolution temperature of 90 ℃, filtered with precision filter paper, and slowly evaporated at 100 ℃ to remove water, 501g of crystals were obtained, purity: 99.5%, particle size of 1-4mm, nitrogen content: 21.11 percent
Example 2.7
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly adding dropwise (dropwise adding speed: 2.30kg/h) 25% ammonia water at 10 deg.C, stopping adding ammonia water when pH value of the system reaches 7, adding 594g ammonia water, and continuing reaction for 20 min. Weighing, using precision filter paper, carrying out vacuum filtration, drying filter residues, and weighing to obtain 10.18g of filter residues. Decolorizing the filtrate for 48h with activated carbon, performing suction filtration again to obtain 1089g of filtrate, transferring into a 2L flask, heating at 104 ℃ for 38min, condensing the steam, weighing, wherein the mass of the condensate is 519g, rectifying to obtain 93g of methanol (boiling range: 64.7-66 ℃), condensing the steam to obtain 503g of white crystals with purity: 88.6%, particle size of 1-2mm, nitrogen content: 20.01 percent. The decolorization procedure was the same as in example 2.1.
Wherein, the rectification process is as follows: the top temperature is 64 ℃, the bottom temperature is 104 ℃, the reflux ratio is 1.0, the top pressure is 101.3KPa, the bottom pressure is 105KPa, the number of tower plates is 6, a wire mesh packing is adopted, the treatment capacity is 50L/h, the height of the tower is 4m, and the inner diameter of the tower is 80 mm.
Example 2.8
Using the system described in example 1.2, 500g of dimethyl sulfate raffinate was charged to a 2.5L three-necked flask. Slowly adding dropwise (dropwise adding speed: 2.30kg/h) 25% ammonia water at 10 deg.C, stopping adding ammonia water when pH value of the system reaches 7, adding 594g ammonia water, and continuing reaction for 20 min. Weighing, using precision filter paper, carrying out vacuum filtration, drying filter residues, and weighing to obtain 10.10g of filter residues. Decolorizing the filtrate for 48h with activated carbon, performing suction filtration again to obtain 1076g of filtrate, transferring to a 2L flask, heating at 100 ℃ for 30min, condensing the steam, weighing, wherein the mass of the condensate is 516g, rectifying to obtain 87g of methanol (boiling range: 64.7-66 ℃), condensing the steam to obtain 499g of white crystals with purity: 89.3%, particle size of 1-2mm, nitrogen content: 20.17 percent. The decolorization procedure was the same as in example 2.1.
Wherein, the rectification process is as follows: the top temperature is 64 ℃, the bottom temperature is 104 ℃, the reflux ratio is 1.5, the top pressure is 101.3KPa, the bottom pressure is 105KPa, the number of tower plates is 5, a wire mesh packing is adopted, the treatment capacity is 50L/h, the height of the tower is 4m, and the inner diameter of the tower is 80 mm.
Comparative example
500g of dimethyl sulfate residue was charged into a 2.5L three-necked flask. Dropwise adding 25% ammonia water at 10 deg.C at a speed of 2.22kg/h, stopping dropwise adding when the pH value of the system reaches 7, reacting for 30min, and drying to obtain black solid 502g with ammonium sulfate content of 76.8%.
In conclusion, the system for preparing the ammonium sulfate and the methanol from the residual liquid of the dimethyl sulfate distillation kettle has the advantages of simple process route, no environmental pollution, capability of separating useful chemical new products such as the ammonium sulfate, the methanol and the like, no generation of new three wastes, safety, environmental protection and better market prospect.
Claims (14)
1. A system for preparing ammonium sulfate and methanol by using dimethyl sulfate distillation kettle residual liquid is characterized by comprising a neutralization reaction unit, a separation unit and a post-treatment unit;
the neutralization reaction unit comprises a neutralization kettle, the feed inlets of the neutralization kettle comprise a raffinate feed inlet and a neutralizing agent feed inlet, and the raffinate feed inlet is connected with a raffinate outlet of the dimethyl sulfate distillation kettle;
the separation unit comprises a filter press, a feed inlet of the filter press is connected with a discharge outlet of the neutralization kettle, and an outlet of the filter press comprises a filtrate outlet and a filter residue outlet;
the post-treatment unit comprises an evaporation kettle and a rectifying tower, a feed inlet of the evaporation kettle is connected with a filtrate outlet of the filter press, a discharge outlet of the evaporation kettle comprises a vapor-phase discharge outlet and a material outlet, the vapor-phase discharge outlet is communicated with a feed inlet of the rectifying tower, and the material outlet obtains ammonium sulfate; the top of the rectifying tower is provided with a solvent outlet, and the bottom of the rectifying tower is provided with a waste liquid outlet;
the material added into the neutralizing agent feed port comprises ammonia water, and preferably, the material added into the neutralizing agent feed port also comprises a flocculating agent.
2. The system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid as claimed in claim 1, wherein a decoloring tower is arranged between the filter press and the evaporation kettle, a feed inlet of the decoloring tower is connected with a filtrate outlet of the filter press, and a discharge outlet of the decoloring tower is connected with a feed inlet of the evaporation kettle.
3. The system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid as claimed in claim 2, wherein a filtering device is arranged between the decoloring tower and the evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the decoloring tower, and a filtrate outlet of the filtering device is connected with a feed inlet of the evaporation kettle.
4. The system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid as claimed in any one of claims 1 to 3, wherein the system further comprises a refining unit, the refining unit comprises a dissolving kettle and a second evaporation kettle, a material inlet of the dissolving kettle is connected with a material outlet of the evaporation kettle of the post-treatment unit, a material outlet of the dissolving kettle is connected with a material inlet of the second evaporation kettle, and the material outlet of the second evaporation kettle obtains ammonium sulfate.
5. The system for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid as claimed in claim 4, wherein a filtering device is arranged between the dissolving kettle and the second evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the dissolving kettle, and a filtrate outlet of the filtering device is connected with a feed inlet of the second evaporation kettle.
6. A method for preparing ammonium sulfate and methanol by using dimethyl sulfate distillation kettle residual liquid is characterized by comprising the following steps:
opening the system for preparing ammonium sulfate and methanol from the dimethyl sulfate distillation still residual liquid as claimed in claim 1, introducing the dimethyl sulfate distillation still residual liquid into the neutralization kettle, adding a neutralizing agent into a feed inlet of the neutralizing agent until the mixed system is neutral, introducing the materials obtained after the reaction into a filter press, introducing the obtained filtrate into an evaporation kettle, evaporating to remove a liquid phase to separate out ammonium sulfate crystals, introducing the vapor-phase substances obtained from the evaporation kettle into a rectifying tower, separating to obtain an organic solvent from the top of the rectifying tower, and obtaining a waste liquid from the bottom of the rectifying tower; preferably, a flocculating agent is also added into the neutralizing agent feed inlet.
7. The method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid according to claim 6, wherein a decoloring tower is arranged between the filter press and the evaporation kettle, a feed inlet of the decoloring tower is connected with a filtrate outlet of the filter press, and a discharge outlet of the decoloring tower is connected with a feed inlet of the evaporation kettle;
wherein, the filtrate of the filter press is introduced into a decoloring tower, and the filtrate is decolored and then introduced into an evaporation kettle.
8. The method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid as claimed in claim 7, wherein a filtering device is arranged between the decoloring tower and the evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the decoloring tower, and a filtrate outlet of the filtering device is connected with a feed inlet of the evaporation kettle;
wherein, the filtrate of the filter press is decolorized and then is introduced into a filtering device, and the filtrate obtained by the filtering device is introduced into an evaporation kettle.
9. The method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residual liquid according to any one of claims 6 to 8, wherein the system further comprises a refining unit, the refining unit comprises a dissolving kettle and a second evaporation kettle, a feed inlet of the dissolving kettle is connected with a material outlet of the evaporation kettle of the post-treatment unit, a discharge outlet of the dissolving kettle is connected with a feed inlet of the second evaporation kettle, and a material outlet of the second evaporation kettle obtains ammonium sulfate;
and (3) introducing crude ammonium sulfate obtained from a material outlet of an evaporation kettle of the post-treatment unit into a dissolving kettle, adding a hydrosolvent, introducing the obtained material into a second evaporation kettle, and separating out refined ammonium sulfate crystals after evaporating a liquid phase.
10. The method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation kettle residual liquid as claimed in claim 9, wherein a filtering device is arranged between the dissolving kettle and the second evaporation kettle, a feed inlet of the filtering device is connected with a discharge outlet of the dissolving kettle, and a filtrate outlet of the filtering device is connected with a feed inlet of the second evaporation kettle;
and introducing the materials obtained in the dissolving kettle into a filtering device, and introducing the obtained filtrate into a second evaporation kettle.
11. The process for producing ammonium sulfate and methanol from dimethyl sulfate still bottoms according to any one of claims 6 to 10, wherein the reaction temperature in the neutralization still is 10 to 90 ℃.
12. The process for producing ammonium sulfate and methanol from dimethyl sulfate distillation still residue as claimed in any one of claims 6 to 11, wherein the temperature of the evaporation vessel of the post-treatment unit is 100 ℃ and 105 ℃.
13. The process for producing ammonium sulfate and methanol from dimethyl sulfate still bottoms according to any one of claims 9 to 12, wherein the temperature of the dissolution tank is 70 to 90 ℃.
14. The method for preparing ammonium sulfate and methanol from dimethyl sulfate distillation still residue according to any one of claims 1 to 13, wherein the parameters of the rectification process of the rectification tower are as follows: the top temperature of the rectifying tower is 64-67 ℃, the bottom temperature of the rectifying tower is 104-105 ℃, the reflux ratio is 1.0-2.0, preferably 1.5-2, and the top pressure: 101.3-103 KPa; kettle pressure: 105KPa 115 KPa; number of trays: 5 to 10, preferably 6 to 10; a wire mesh packing is adopted.
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| US4229596A (en) * | 1970-03-05 | 1980-10-21 | The Goodyear Tire & Rubber Company | Process for the continuous isolation of dihydric phenols |
| RU2504534C1 (en) * | 2012-12-26 | 2014-01-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП "ГНИИХТЭОС") | Method of producing methyl chloride |
| CN105170046A (en) * | 2015-07-23 | 2015-12-23 | 百川化工(如皋)有限公司 | DMP neutralizing treatment method |
| US20180071653A1 (en) * | 2015-03-25 | 2018-03-15 | Stamicarbon B.V. | Integrated production of urea for diesel exhaust fluid and urea ammonium nitrate |
| CN109336736A (en) * | 2018-09-07 | 2019-02-15 | 重庆大学 | Desalination continuous process before a kind of steaming of resource utilization BDO device waste liquid |
| CN210009952U (en) * | 2019-04-01 | 2020-02-04 | 湖北富博化工有限责任公司 | Residue processing apparatus is used in dimethyl sulfate production |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229596A (en) * | 1970-03-05 | 1980-10-21 | The Goodyear Tire & Rubber Company | Process for the continuous isolation of dihydric phenols |
| RU2504534C1 (en) * | 2012-12-26 | 2014-01-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП "ГНИИХТЭОС") | Method of producing methyl chloride |
| US20180071653A1 (en) * | 2015-03-25 | 2018-03-15 | Stamicarbon B.V. | Integrated production of urea for diesel exhaust fluid and urea ammonium nitrate |
| CN105170046A (en) * | 2015-07-23 | 2015-12-23 | 百川化工(如皋)有限公司 | DMP neutralizing treatment method |
| CN109336736A (en) * | 2018-09-07 | 2019-02-15 | 重庆大学 | Desalination continuous process before a kind of steaming of resource utilization BDO device waste liquid |
| CN210009952U (en) * | 2019-04-01 | 2020-02-04 | 湖北富博化工有限责任公司 | Residue processing apparatus is used in dimethyl sulfate production |
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