CN116143143B - Method and device for recycling waste salt and waste sulfuric acid in BDO production - Google Patents
Method and device for recycling waste salt and waste sulfuric acid in BDO production Download PDFInfo
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- CN116143143B CN116143143B CN202211217361.2A CN202211217361A CN116143143B CN 116143143 B CN116143143 B CN 116143143B CN 202211217361 A CN202211217361 A CN 202211217361A CN 116143143 B CN116143143 B CN 116143143B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 239000002699 waste material Substances 0.000 title claims abstract description 89
- 150000003839 salts Chemical class 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004064 recycling Methods 0.000 title claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000012528 membrane Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 86
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 53
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 53
- 235000011152 sodium sulphate Nutrition 0.000 claims description 53
- 239000000919 ceramic Substances 0.000 claims description 46
- 238000003860 storage Methods 0.000 claims description 44
- 238000001914 filtration Methods 0.000 claims description 43
- 239000002904 solvent Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000012267 brine Substances 0.000 claims description 18
- 239000000498 cooling water Substances 0.000 claims description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of three-waste treatment, in particular to a method and a device for recycling waste salt and waste sulfuric acid in BDO production, which are characterized in that waste acid and waste salt in the BDO device production process are subjected to filter pressing, membrane separation, crystallization, dissolution, electrolysis and other process technologies to produce 98% concentrated sulfuric acid and 32% sodium hydroxide solution, and the concentrated sulfuric acid and the 32% sodium hydroxide solution are returned to BDO production for reuse, so that the waste recycling is realized. The invention has simple process method and convenient use, can reduce the consumption of materials on one hand and save the treatment cost of wastes on the other hand by recycling waste residues and waste liquid, effectively controls the production cost, and has the characteristics of safety, labor saving, simplicity, convenience and high efficiency.
Description
Technical Field
The invention relates to the technical field of three-waste treatment, in particular to a method and a device for recycling waste salt and waste sulfuric acid in BDO production.
Background
2-Butanediol (BDO) is a chemical of formula C 4 H 1 0O 2 The method is mainly used for organic synthesis, preparation of 2-aminobutanol and the like. The main uses of 1, 2-butanediol are as a diol monomer modified by polyester and polyurethane resins and as a plasticizer production raw material for PVC resins. Present BDODuring the production process, waste sulfuric acid (78% to 82%) and waste liquid and waste salt (a mixture of 88% to 94% sodium carbonate, 2% to 4% sodium sulfate and 5% to 8% sodium hydroxide solids) generated by waste liquid and waste gas treatment are generated. Therefore, the material consumption is high, and meanwhile, a great amount of manpower and material resources are input for waste treatment, so that the production cost of enterprises is increased, and the environmental protection is also greatly hidden trouble.
Disclosure of Invention
The invention provides a method and a device for recycling waste salt and waste sulfuric acid in BDO production, which overcome the defects of the prior art, and can effectively solve the problems that wastes in the prior BDO production cannot be treated and the production cost is high.
One of the technical schemes of the invention is realized by the following measures: the method for recycling the waste salt and the waste sulfuric acid in BDO production is carried out according to the following steps: firstly, adding a waste sulfuric acid solution and waste salt in the BDO production process into a reactor, and carrying out a neutralization reaction on the waste sulfuric acid solution and the waste salt by taking desalted water as a solvent for reaction to obtain crude brine of sodium sulfate and carbon dioxide gas; secondly, the carbon dioxide is discharged after being collected and treated, insoluble substances are filtered out from crude brine of sodium sulfate through a crude filter, and the filtered sodium sulfate solution is subjected to further filtration on tiny insoluble substances through a filter press, so that a primary sodium sulfate solution is obtained through filtration; thirdly, purifying the primary sodium sulfate solution by low-temperature crystallization of a crystallizer to remove calcium and magnesium ions in the solution, and returning the crystallized supernatant to the reactor through a first solvent circulation pipeline and a second solvent circulation pipeline to a solvent conveying pipeline respectively to serve as a solvent for recycling, wherein the crystallized sodium sulfate solid is dissolved by desalted water to obtain a refined secondary sodium sulfate solution; fourthly, filtering the refined secondary sodium sulfate solution through a ceramic membrane filter to further remove metal ion impurities and obtain a pure sodium sulfate aqueous solution; fifthly, the pure sodium sulfate aqueous solution enters an electrolytic tank, and 110KV voltage is introduced for electrolysis to obtain sodium hydroxide aqueous solution and dilute sulfuric acid solution; and sixthly, conveying the sodium hydroxide aqueous solution to a tank field for storage, and then conveying the sodium hydroxide aqueous solution back to a BDO production device for use, wherein the dilute sulfuric acid solution is recovered and purified to obtain a concentrated sulfuric acid solution, and conveying the concentrated sulfuric acid solution back to BDO production for use after the concentrated sulfuric acid solution is stored in the tank field.
The following are further optimizations and/or improvements to one of the above-described inventive solutions:
in the first step, the mass percentage of the waste sulfuric acid solution is 78-82%, and the waste salt is a mixture of sodium carbonate solid, sodium sulfate solid and sodium hydroxide solid, wherein the mass percentage of the sodium carbonate solid, the sodium sulfate solid and the sodium hydroxide solid in the mixture is 88-94%, 2-4% and 5-8%, respectively.
In the third step, the mass percentage of the refined secondary sodium sulfate solution is 2 to 36 percent; or/and, in the fifth step, the mass percentage of the obtained sodium hydroxide aqueous solution is 32%, and the mass percentage of the dilute sulfuric acid solution is 10%; or/and, in the sixth step, the mass percentage of the concentrated sulfuric acid solution is 98%.
The second technical scheme of the invention is realized by the following measures: a device for implementing a method for recycling waste salt and waste sulfuric acid in BDO production comprises a waste sulfuric acid storage tank, a waste salt storage tank, a reactor, a first coarse filter, a first filter press, a first crystallizer, a first ceramic membrane filter, a refined sodium sulfate solution storage tank, an electrolytic tank, a sulfuric acid concentration tank, an alkali liquor storage tank and a concentrated sulfuric acid storage tank, wherein a waste sulfuric acid conveying pipeline is fixedly communicated between an outlet at the bottom of the waste sulfuric acid storage tank and a first inlet at the upper part of the reactor, a waste salt conveying pipeline is fixedly communicated between an outlet at the bottom of the waste salt storage tank and an inlet at the top of the reactor, a first coarse filter pipeline is fixedly communicated between an outlet at the bottom of the reactor and an inlet at the upper part of the first coarse filter, a first filter pressing pipeline is fixedly communicated between an outlet at the bottom of the first coarse filter and an inlet of the first filter press, a first crystallization pipeline is fixedly communicated between an outlet at the first filter press and an inlet at the upper part of the first ceramic membrane filter, a first refined sodium sulfate solution conveying pipeline is fixedly communicated between an outlet at the bottom of the first ceramic membrane filter and an inlet at the upper part of the first concentrated sulfuric acid storage tank, a dilute sulfuric acid conveying pipeline is fixedly communicated between an outlet at the bottom of the first filter and an outlet at the upper part of the first ceramic membrane filter and an inlet at the first storage tank, a concentrated sulfuric acid conveying pipeline is fixedly communicated between a concentrated sulfuric acid solution conveying pipeline is fixedly communicated between an outlet at the bottom of the first filter and an outlet at the top of the first filter and an outlet at the first storage tank and an outlet at the top of the first storage tank, and an outlet at the concentrated sulfuric acid outlet is fixedly communicated with a concentrated sulfuric acid conveying pipeline is fixedly communicated between an inlet is, and a weighing meter is fixedly arranged on the waste salt conveying pipeline.
The following is a further optimization and/or improvement of the second technical scheme of the invention:
the filter press further comprises a second coarse filter, a second filter press, a second crystallizer and a second ceramic membrane filter, wherein a second coarse filter pipeline is fixedly communicated between the first coarse filter pipeline and an inlet at the upper part of the second coarse filter, a second filter pressing pipeline is fixedly communicated between an outlet at the bottom of the second coarse filter and an inlet of the second filter press, a second crystallization pipeline is fixedly communicated between an outlet of the second filter press and an inlet of the second crystallizer, a second fine filter pipeline is fixedly communicated between an outlet of the second crystallizer and an inlet at the upper part of the second ceramic membrane filter, and a second solution filtered pipeline is fixedly communicated between an outlet at the bottom of the second ceramic membrane filter and the first fine filter pipeline.
The first coarse filtration conveying pump is fixedly arranged on the first coarse filtration pipeline between the second coarse filtration pipeline and the first coarse filter, and the second coarse filtration conveying pump is fixedly arranged on the second coarse filtration pipeline.
And a third coarse filter pipeline is fixedly communicated between a second coarse filter pipeline between the second coarse filter conveying pump and the second coarse filter and a first coarse filter pipeline between the first coarse filter conveying pump and the first coarse filter.
The waste sulfuric acid conveying pipeline is fixedly provided with a waste sulfuric acid conveying pump, the first electrolytic conveying pipeline is fixedly provided with a first electrolytic conveying pump, a second electrolytic conveying pipeline is fixedly communicated between the first electrolytic conveying pipeline between the first electrolytic conveying pump and the refined sodium sulfate solution storage tank and the first electrolytic conveying pipeline between the first electrolytic conveying pump and the electrolytic tank, and the second electrolytic conveying pipeline is fixedly provided with a second electrolytic conveying pump.
The reactor is internally provided with a stirrer, the outer wall of the reactor is provided with a cooling water jacket, an inlet of the cooling water jacket is fixedly communicated with a cooling water inlet pipeline, an outlet of the cooling water jacket is fixedly communicated with a cooling water outlet pipeline, the bottom of the reactor is provided with a first pH meter, and outlets of the bottoms of the first ceramic membrane filter and the second ceramic membrane filter are respectively provided with a second pH meter and an ion detector.
The first brine return pipeline is fixedly communicated between the first solution filtered pipeline and the first fine filtering pipeline between the first ceramic membrane filter and the second solution filtered pipeline, the second brine return pipeline is fixedly communicated between the second solution filtered pipeline and the second fine filtering pipeline, the first solvent circulating pipeline is fixedly communicated with the liquid outlet at the upper part of the first crystallizer, and the second solvent circulating pipeline is fixedly communicated with the liquid outlet at the upper part of the second crystallizer.
The excellent effects of the invention are as follows:
1. the resource utilization of the waste can be realized, the consumption of materials can be reduced, the treatment cost of the waste can be saved, and the production cost can be effectively controlled;
2. the method has the advantages of simple equipment construction and short process flow, and provides necessary technical support for industrialized development;
3. the method is favorable for quickly solving the problem of waste treatment in the BDO production process, and has remarkable efficiency in improving the environment management.
Drawings
Fig. 1 is a schematic structural diagram of a process flow in embodiment 4 of the present invention.
The codes in fig. 1 are respectively: 1 is a spent sulfuric acid storage tank, 2 is a spent salt storage tank, 3 is a reactor, 4 is a first coarse filter, 5 is a first filter press, 6 is a first crystallizer, 7 is a first ceramic membrane filter, 8 is a refined sodium sulfate solution storage tank, 9 is an electrolytic tank, 10 is a sulfuric acid concentrating tank, 11 is an alkali liquor storage tank, 12 is a concentrated sulfuric acid storage tank, 13 is a spent sulfuric acid conveying line, 14 is a spent salt conveying line, 15 is a first coarse filter line, 16 is a first filter pressing line, 17 is a first crystallization line, 18 is a first fine filter line, 19 is a first solution post-filtration line, 20 is a first electrolytic conveying line, 21 is a dilute sulfuric acid conveying line, 22 is a concentrated sulfuric acid conveying line, 23 is an alkali liquor conveying line, 24 is a gas discharge line, 25 is a solvent conveying line, 26 is a scale meter, 27 is a second coarse filter, 28 is a second filter press, 29 is a second crystallizer, 30 is a second ceramic membrane filter, 31 is a second coarse filtration line, 32 is a second press filtration line, 33 is a second crystallization line, 34 is a second fine filtration line, 35 is a second solution post-filtration line, 36 is a first coarse filtration transfer pump, 37 is a second coarse filtration transfer pump, 38 is a third coarse filtration line, 39 is a spent sulfuric acid transfer pump, 40 is a first electrolytic transfer pump, 41 is a second electrolytic transfer line, 42 is a second electrolytic transfer pump, 43 is a stirrer, 44 is a cooling water inlet line, 45 is a cooling water outlet line, 46 is a second solvent circulation line, 47 is a first solvent circulation line, 48 is a second pH meter, 49 is an ion detector, 50 is a first brine return line, 51 is a second brine return line, 52 is a first pH meter.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments can be determined according to the technical scheme and practical situations of the present invention. The various chemical reagents and chemical supplies mentioned in the invention are all commonly known and used in the prior art unless specified otherwise; the room temperature and the room temperature in the present invention generally refer to temperatures ranging from 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to examples and figures:
example 1: the method for recycling the waste salt and the waste sulfuric acid in BDO production is carried out according to the following steps: firstly, adding a waste sulfuric acid solution and waste salt in the BDO production process into a reactor, and carrying out a neutralization reaction on the waste sulfuric acid solution and the waste salt by taking desalted water as a solvent for reaction to obtain crude brine of sodium sulfate and carbon dioxide gas; secondly, the carbon dioxide is discharged after being collected and treated, insoluble substances are filtered out from crude brine of sodium sulfate through a crude filter, and the filtered sodium sulfate solution is subjected to further filtration on tiny insoluble substances through a filter press, so that a primary sodium sulfate solution is obtained through filtration; thirdly, purifying the primary sodium sulfate solution by low-temperature crystallization of a crystallizer to remove calcium and magnesium ions in the solution, and returning the crystallized supernatant to the reactor through a first solvent circulation pipeline and a second solvent circulation pipeline to a solvent conveying pipeline respectively to serve as a solvent for recycling, wherein the crystallized sodium sulfate solid is dissolved by desalted water to obtain a refined secondary sodium sulfate solution; fourthly, filtering the refined secondary sodium sulfate solution through a ceramic membrane filter to further remove metal ion impurities and obtain a pure sodium sulfate aqueous solution; fifthly, the pure sodium sulfate aqueous solution enters an electrolytic tank, and 110KV voltage is introduced for electrolysis to obtain sodium hydroxide aqueous solution and dilute sulfuric acid solution; and sixthly, conveying the sodium hydroxide aqueous solution to a tank field for storage, and then conveying the sodium hydroxide aqueous solution back to a BDO production device for use, wherein the dilute sulfuric acid solution is recovered and purified to obtain a concentrated sulfuric acid solution, and conveying the concentrated sulfuric acid solution back to BDO production for use after the concentrated sulfuric acid solution is stored in the tank field.
Example 2: as an optimization of the above embodiment, in the first step, the mass percentage of the waste sulfuric acid solution is 78% to 82%, and the waste salt is a mixture of sodium carbonate solid, sodium sulfate solid and sodium hydroxide solid, wherein in the mixture, the mass percentage of the sodium carbonate solid, sodium sulfate solid and sodium hydroxide solid is 88% to 94%, 2% to 4%, and 5% to 8%, respectively.
Example 3: as an optimization of the above embodiment, in the third step, the mass percentage of the refined secondary sodium sulfate solution is 2% to 36%; or/and, in the fifth step, the mass percentage of the obtained sodium hydroxide aqueous solution is 32%, and the mass percentage of the dilute sulfuric acid solution is 10%; or/and, in the sixth step, the mass percentage of the concentrated sulfuric acid solution is 98%.
Example 4: as shown in figure 1, the device for implementing the method for recycling the waste salt and the waste sulfuric acid in BDO production comprises a waste sulfuric acid storage tank, a waste salt storage tank, a reactor, a first coarse filter, a first filter press, a first crystallizer, a first ceramic membrane filter, a refined sodium sulfate solution storage tank, an electrolytic tank, a sulfuric acid concentration tank, an alkali liquor storage tank and a concentrated sulfuric acid storage tank, wherein a waste sulfuric acid conveying pipeline is fixedly communicated between the bottom outlet of the waste sulfuric acid storage tank and a first inlet at the upper part of the reactor, a waste salt conveying pipeline is fixedly communicated between the bottom outlet of the waste salt storage tank and the inlet at the top of the reactor, a first coarse filter pipeline is fixedly communicated between the bottom outlet of the reactor and the upper inlet of the first coarse filter, a first filter pressing pipeline is fixedly communicated between the bottom outlet of the first coarse filter press and the inlet of the first crystallizer, a first fine filtration pipeline is fixedly communicated between the outlet of the first crystallizer and the upper inlet of the first ceramic membrane filter, a first solution filtered pipeline is fixedly communicated between the outlet of the bottom of the first ceramic membrane filter and the upper inlet of the refined sodium sulfate solution storage tank, a first electrolysis conveying pipeline is fixedly communicated between the outlet of the bottom of the refined sodium sulfate solution storage tank and the inlet of the electrolytic tank, a dilute sulfuric acid conveying pipeline is fixedly communicated between the outlet of the electrolytic tank acid liquid outlet and the inlet of the sulfuric acid concentrating tank, a concentrated sulfuric acid conveying pipeline is fixedly communicated between the outlet of the sulfuric acid concentrating tank and the inlet of the concentrated sulfuric acid storage tank, an alkali conveying pipeline is fixedly communicated between the alkali liquid outlet of the electrolytic tank and the alkali liquid storage tank, a gas exhaust pipeline is fixedly communicated at the outlet of the top of the reactor, a solvent conveying pipeline is fixedly communicated at the upper second inlet of the reactor, and a weighing meter is fixedly arranged on the waste salt conveying pipeline.
In practice of the invention, the scale 26 may be claimed to be fed into the reactor 3 at a flow rate of 300kg/h to 350kg/h, and the spent acid may be metered by a mass flow meter to the reactor 3 at a flow rate of 450kg/h to 500 kg/h.
Example 5: which differs from example 4 in that: as shown in fig. 1, the device further comprises a second coarse filter 27, a second filter press 28, a second crystallizer 29 and a second ceramic membrane filter 30, wherein a second coarse filter pipeline 31 is fixedly communicated between the first coarse filter pipeline 15 and an upper inlet of the second coarse filter 27, a second filter pressing pipeline 32 is fixedly communicated between an outlet at the bottom of the second coarse filter 27 and an inlet of the second filter press 28, a second crystallization pipeline 33 is fixedly communicated between an outlet of the second filter press 28 and an inlet of the second crystallizer 29, a second fine filter pipeline 34 is fixedly communicated between an outlet of the second crystallizer 29 and an upper inlet of the second ceramic membrane filter 30, and a second solution filtered pipeline 35 is fixedly communicated between an outlet at the bottom of the second ceramic membrane filter 30 and the first solution filtered pipeline 19.
In the invention, three-stage filtration, primary coarse filtration, interception of insoluble substances in the solution, secondary filter press, further filtration of suspended substances and small particles in the solution, and three-stage filtration by adopting a ceramic membrane, wherein a novel polymer membrane material is adopted as a material of a filter element, and only sodium sulfate aqueous solution is allowed to pass through, so that the aim of removing impurities is fulfilled.
The second coarse filter 27, the second filter press 28, the second crystallizer 29 and the second ceramic membrane filter 30 can be respectively switched to the first coarse filter 4, the first filter press 5, the first crystallizer 6 and the first ceramic membrane filter 7 according to the requirements, so that stable production of the continuous process can be ensured.
Example 6: which differs from examples 4 to 5 in that: as shown in fig. 1, a first coarse filtration transfer pump 36 is fixedly installed on the first coarse filtration line 15 between the second coarse filtration line 31 and the first coarse filtration 4, and a second coarse filtration transfer pump 37 is fixedly installed on the second coarse filtration line 31.
Example 7: which differs from examples 4 to 6 in that: as shown in fig. 1, a third coarse filter line 38 is fixedly connected between the second coarse filter line 31 between the second coarse filter transfer pump 37 and the second coarse filter 27 and the first coarse filter line 15 between the first coarse filter transfer pump 36 and the first coarse filter 4.
Example 8: which differs from examples 4 to 7 in that: as shown in fig. 1, a waste sulfuric acid conveying pump 39 is fixedly arranged on the waste sulfuric acid conveying pipeline 13, a first electrolytic conveying pump 40 is fixedly arranged on the first electrolytic conveying pipeline 20, a second electrolytic conveying pipeline 41 is fixedly communicated between the first electrolytic conveying pipeline 20 between the first electrolytic conveying pump 40 and the refined sodium sulfate solution storage tank 8 and the first electrolytic conveying pipeline 20 between the first electrolytic conveying pump 40 and the electrolytic tank 9, and a second electrolytic conveying pump 42 is fixedly arranged on the second electrolytic conveying pipeline 41.
Example 9: which differs from examples 4 to 8 in that: as shown in fig. 1, a stirrer 43 is arranged in the reactor 3, a cooling water jacket is arranged on the outer wall of the reactor 3, a cooling water inlet pipeline 44 is fixedly communicated with an inlet of the cooling water jacket, a cooling water outlet pipeline 45 is fixedly communicated with an outlet of the cooling water jacket, a first pH meter 52 is arranged at the bottom of the reactor, and a second pH meter 48 and an ion detector 49 are arranged at the outlets of the bottoms of the first ceramic membrane filter 7 and the second ceramic membrane filter 30.
The stirrer 43 in the reactor 3 and the cooling water jacket on the outer wall can uniformly remove heat in the reactor 3 according to the requirement, so as to prevent heat aggregation. The first pH meter 52 can monitor the pH of the post-reaction solution in the reactor 3 to between 6 and 6.5 to ensure that the complete reaction of the waste salts is completed.
Example 10: which differs from examples 1 to 9 in that: as shown in fig. 1, a first brine return line 50 is fixedly connected between the first solution filtered pipeline 19 and the first fine filtration pipeline 18 between the first ceramic membrane filter 7 and the second solution filtered pipeline 35, a second brine return line 51 is fixedly connected between the second solution filtered pipeline 35 and the second fine filtration pipeline 34, a first solvent circulation pipeline 47 is fixedly connected with an upper liquid outlet of the first crystallizer 6, and a second solvent circulation pipeline 46 is fixedly connected with an upper liquid outlet of the second crystallizer 29.
According to the requirement, a second pH meter 48 and an ion detector 49 may be disposed at the outlet of the first ceramic membrane filter 7 and the second ceramic membrane filter 30, and if the parameter values of the secondary brine discharged from the first ceramic membrane filter 7 and the second ceramic membrane filter 30 deviate from the set numerical indexes, the secondary brine discharged from the first ceramic membrane filter 7 and the second ceramic membrane filter 30 is returned to the first ceramic membrane filter 7 and the second ceramic membrane filter 30 through a first brine return line 50 and a second brine return line 51 respectively, so as to ensure that the solution filtered by the first ceramic membrane filter 7 and the second ceramic membrane filter 30 meets the process requirements.
According to the requirements, the device for implementing the method for recycling the waste salt and the waste sulfuric acid in BDO production is fixedly provided with conventional valves, pressure gauges, temperature gauges, liquid level gauges and the like which can enable the device to normally operate.
In summary, the process method is simple, the device is convenient to use, and the waste residue and the waste liquid are recycled, so that the material consumption can be reduced, the waste treatment cost can be saved, the production cost can be effectively controlled, and the method has the characteristics of safety, labor saving, simplicity, convenience and high efficiency.
The technical characteristics form the embodiment of the invention, have stronger adaptability and implementation effect, and can increase or decrease unnecessary technical characteristics according to actual needs so as to meet the requirements of different situations.
Claims (6)
1. A method for recycling waste salt and waste sulfuric acid in BDO production is characterized by comprising the following steps: firstly, adding a waste sulfuric acid solution and waste salt in the BDO production process into a reactor, and carrying out a neutralization reaction on the waste sulfuric acid solution and the waste salt by taking desalted water as a solvent of the reaction to obtain coarse brine of sodium sulfate and carbon dioxide gas, wherein the mass percent of the waste sulfuric acid solution is 78-82%, and the waste salt is a mixture of sodium carbonate solid, sodium sulfate solid and sodium hydroxide solid, and the mass percent of the sodium carbonate solid, the sodium sulfate solid and the sodium hydroxide solid in the mixture is 88-94%, 2-4% and 5-8%, respectively; secondly, the carbon dioxide is discharged after being collected and treated, insoluble substances are filtered out from crude brine of sodium sulfate through a crude filter, and the filtered sodium sulfate solution is subjected to further filtration on tiny insoluble substances through a filter press, so that a primary sodium sulfate solution is obtained through filtration; thirdly, purifying the primary sodium sulfate solution by low-temperature crystallization of a crystallizer to remove calcium and magnesium ions in the solution, and returning crystallized supernatant to the reactor through a first solvent circulation pipeline and a second solvent circulation pipeline to a solvent conveying pipeline to serve as a solvent for recycling, wherein crystallized sodium sulfate solid is dissolved by desalted water to obtain a refined secondary sodium sulfate solution, and the mass percent of the refined secondary sodium sulfate solution is 2-36%; fourthly, filtering the refined secondary sodium sulfate solution through a ceramic membrane filter to further remove metal ion impurities and obtain a pure sodium sulfate aqueous solution; fifthly, the pure sodium sulfate aqueous solution enters an electrolytic tank, 110KV voltage is introduced for electrolysis, and sodium hydroxide aqueous solution and dilute sulfuric acid solution are obtained, wherein the mass percentage of the sodium hydroxide aqueous solution is 32%, and the mass percentage of the dilute sulfuric acid solution is 10%; and sixthly, conveying the sodium hydroxide aqueous solution to a tank field for storage, and then conveying the sodium hydroxide aqueous solution back to a BDO production device for use, wherein the dilute sulfuric acid solution is recovered and purified to obtain a concentrated sulfuric acid solution, and conveying the concentrated sulfuric acid solution back to BDO production for use after the concentrated sulfuric acid solution is stored in the tank field for washing and purifying acetylene gas, wherein the mass percentage of the concentrated sulfuric acid solution is 98%.
2. An apparatus for carrying out the method for recycling waste salt and waste sulfuric acid in BDO production according to claim 1, characterized by comprising a waste sulfuric acid storage tank, a waste salt storage tank, a reactor, a first coarse filter, a first filter press, a first crystallizer, a first ceramic membrane filter, a refined sodium sulfate solution storage tank, an electrolytic tank, a sulfuric acid concentration tank, an alkali liquor storage tank and a concentrated sulfuric acid storage tank, wherein a waste sulfuric acid conveying pipeline is fixedly communicated between the bottom outlet of the waste sulfuric acid storage tank and the first inlet at the upper part of the reactor, a waste salt conveying pipeline is fixedly communicated between the bottom outlet of the waste salt storage tank and the top inlet of the reactor, a first coarse filter pipeline is fixedly communicated between the bottom outlet of the reactor and the upper inlet of the first coarse filter, a first filter pressing pipeline is fixedly communicated between the bottom outlet of the first coarse filter and the inlet of the first filter press, a first crystallization pipeline is fixedly communicated between the outlet of the first filter press and the inlet of the first crystallizer, a first fine filtration pipeline is fixedly communicated between the outlet of the first crystallizer and the inlet at the upper part of the first ceramic membrane filter, a first solution filtered pipeline is fixedly communicated between the outlet at the bottom of the first ceramic membrane filter and the inlet at the upper part of the refined sodium sulfate solution storage tank, a first electrolysis conveying pipeline is fixedly communicated between the outlet at the bottom of the refined sodium sulfate solution storage tank and the inlet of the electrolytic tank, a dilute sulfuric acid conveying pipeline is fixedly communicated between the outlet of the electrolytic tank and the inlet of the sulfuric acid concentrating tank, a concentrated sulfuric acid conveying pipeline is fixedly communicated between the outlet of the sulfuric acid concentrating tank and the inlet of the concentrated sulfuric acid storage tank, an alkali conveying pipeline is fixedly communicated between the outlet of the electrolytic tank and the alkali storage tank, a gas discharge pipeline is fixedly communicated at the outlet at the top of the reactor, a solvent conveying pipeline is fixedly communicated at the second inlet at the upper part of the reactor, the device also comprises a second coarse filter, a second filter press, a second crystallizer and a second ceramic membrane filter, wherein the second coarse filter is fixedly communicated with an inlet at the upper part of the second coarse filter, a second filter pressing pipeline is fixedly communicated between an outlet at the bottom of the second coarse filter and an inlet of the second filter press, a second crystallization pipeline is fixedly communicated between an outlet of the second filter press and an inlet at the upper part of the second crystallizer, a second fine filter pipeline is fixedly communicated between an outlet of the second crystallizer and an inlet at the upper part of the second ceramic membrane filter, a second solution filtered pipeline is fixedly communicated between an outlet at the bottom of the second ceramic membrane filter and the first fine filter pipeline, a first brine return pipeline is fixedly communicated between a first solution filtered pipeline between the first ceramic membrane filter and the second solution filtered pipeline and the first fine filter pipeline, a second brine return pipeline is fixedly communicated between the second solution filtered pipeline and the second fine filter pipeline, a first solvent circulating pipeline is fixedly communicated with a liquid outlet at the upper part of the first crystallizer, and a second solvent circulating pipeline is fixedly communicated with a liquid outlet at the upper part of the second crystallizer.
3. The apparatus of claim 2, wherein a first coarse filtration transfer pump is fixedly mounted on the first coarse filtration line between the second coarse filtration line and the first coarse filter, and a second coarse filtration transfer pump is fixedly mounted on the second coarse filtration line.
4. A device according to claim 3, characterized in that a third coarse filter line is fixedly connected between the second coarse filter line between the second coarse filter transfer pump and the second coarse filter and the first coarse filter line between the first coarse filter transfer pump and the first coarse filter.
5. The apparatus according to claim 2, 3 or 4, wherein the waste sulfuric acid conveying pipeline is fixedly provided with a waste sulfuric acid conveying pump, the first electrolytic conveying pipeline is fixedly provided with a first electrolytic conveying pump, a second electrolytic conveying pipeline is fixedly communicated between the first electrolytic conveying pipeline between the first electrolytic conveying pump and the refined sodium sulfate solution storage tank and the first electrolytic conveying pipeline between the first electrolytic conveying pump and the electrolytic tank, and the second electrolytic conveying pipeline is fixedly provided with a second electrolytic conveying pump.
6. The device according to claim 2, 3 or 4, wherein a stirrer is arranged in the reactor, a cooling water jacket is arranged on the outer wall of the reactor, a cooling water inlet pipeline is fixedly communicated with an inlet of the cooling water jacket, a cooling water outlet pipeline is fixedly communicated with an outlet of the cooling water jacket, a first pH meter is arranged at the bottom of the reactor, and a second pH meter and an ion detector are arranged at the outlets of the bottoms of the first ceramic membrane filter and the second ceramic membrane filter.
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| CA2930096A1 (en) * | 2007-09-20 | 2009-03-26 | Skyonic Corporation | Removing carbon dioxide from waste streams through co-generation of carbonate and/or bicarbonate minerals |
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| CN101244831A (en) * | 2008-03-18 | 2008-08-20 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
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