CN114539031B - Device and method for removing tar from m-phenylenediamine acidic hydrolysate - Google Patents
Device and method for removing tar from m-phenylenediamine acidic hydrolysate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 51
- 239000000413 hydrolysate Substances 0.000 title claims abstract description 47
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229940018564 m-phenylenediamine Drugs 0.000 title claims abstract description 40
- 239000012528 membrane Substances 0.000 claims abstract description 110
- 239000000919 ceramic Substances 0.000 claims abstract description 109
- 239000000706 filtrate Substances 0.000 claims abstract description 28
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 238000003825 pressing Methods 0.000 claims abstract description 19
- 239000006228 supernatant Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 8
- -1 diiodo-amino Chemical group 0.000 claims description 8
- 238000005374 membrane filtration Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 37
- 239000000047 product Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 21
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000004062 sedimentation Methods 0.000 abstract description 7
- 238000004821 distillation Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000005238 degreasing Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007670 refining Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011269 tar Substances 0.000 description 95
- 239000003921 oil Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 108010009736 Protein Hydrolysates Proteins 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229940018563 3-aminophenol Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NYPYHUZRZVSYKL-UHFFFAOYSA-N -3,5-Diiodotyrosine Natural products OC(=O)C(N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-UHFFFAOYSA-N 0.000 description 1
- NYPYHUZRZVSYKL-ZETCQYMHSA-N 3,5-diiodo-L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC(I)=C(O)C(I)=C1 NYPYHUZRZVSYKL-ZETCQYMHSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a device and a method for removing tar from m-phenylenediamine acidic hydrolysate. The method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps: 1. settling and deoiling the m-phenylenediamine acidic hydrolysate; 2. removing large-particle carbon powder and a small amount of tar by using a plate-and-frame filter press; 3. the temperature of the filtrate after the plate and frame filter pressing is reduced to 20-30 ℃; 4. tar in the acidic hydrolysate is removed by utilizing the high-precision degreasing performance of the super-hydrophilic ceramic membrane. The ceramic membrane degreasing technology is combined with the traditional sedimentation and plate-frame filter pressing method, so that the tar content in the m-phenylenediamine acidic hydrolysate is obviously reduced, the problems of reduced extraction and distillation efficiency, even process interruption and pipeline blockage caused by overhigh tar content in the extraction and refining processes of resorcinol products are solved, and the recycled water is increased; not only reduces the running cost and improves the product quality and the recovery rate, but also reduces the discharge capacity, thereby being beneficial to environmental protection.
Description
Technical Field
The invention relates to a device and a method for removing tar from m-phenylenediamine acidic hydrolysate, belonging to the technical field of chemical separation.
Background
At present, the resorcinol production by m-phenylenediamine in strong acid environment through high-temperature hydrolysis is gradually becoming the mainstream and mature process of the resorcinol product production method, and the method has the outstanding characteristics of one-step reaction, few byproducts and mild conditions, and the produced byproducts are ammonium sulfate and a small amount of tar, so that the environmental pollution is relatively less.
However, m-phenylenediamine is hydrolyzed under acidic conditions to obtain resorcinol as a main product, and m-aminophenol, a small amount of tar, inorganic salts and other byproducts are also added, so that the byproducts need to be removed in order to obtain a purer product, the m-aminophenol can be separated from resorcinol by acidic dissolution and extraction, a small amount of tar is generally removed by adsorption with activated carbon, and the inorganic salts can be recovered by multi-effect evaporation. The process for separating the byproducts has better separation effect. However, the tar separation has the following disadvantages:
1) The tar removal process can only be carried out in the aqueous phase after the extraction process, otherwise the activated carbon adsorbs a large amount of resorcinol products, and during the extraction process, the presence of a large amount of tar results in low extraction efficiency, sometimes even impossible to carry out and stop, resulting in product loss and low yield.
2) In the reduced pressure distillation process of the extract phase, the distillation is affected due to the existence of a certain amount of tar, and the quality of the product is directly affected.
3) The more harmful is that the tar content can cause serious carbon accumulation in the pipeline and equipment, and the pipeline and the equipment can be directly blocked.
4) The recycling rate of the wastewater is reduced, and the discharge capacity is increased.
5) After the activated carbon is adsorbed and saturated, a plurality of waste activated carbon dangerous articles can be formed, and the risk of environmental injury is increased.
In order to solve the problems, the invention provides a method for removing tar in m-phenylenediamine acidic hydrolysate by adopting a ceramic membrane integration technology.
Disclosure of Invention
The invention provides a device and a method for removing tar from m-phenylenediamine acidic hydrolysate, which combine a hydrophilic ceramic membrane with the traditional sedimentation and plate-and-frame process by utilizing the characteristic of high retention rate of tar in the super-hydrophilic ceramic membrane to the m-phenylenediamine acidic hydrolysate, so as to achieve the aim of removing tar in the m-phenylenediamine acidic hydrolysate; the tar content can be reduced to the minimum, the smooth operation of the extraction and distillation of the next process is greatly facilitated, the recovery rate of the product is improved, the application frequency of the waste water is increased, the discharge amount of the waste water and the waste activated carbon is reduced, and the method has great economic and environmental protection significance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Settling and deoiling the m-phenylenediamine acidic hydrolysate;
2) Pre-filtering the supernatant obtained in the step 1) by adopting a plate-and-frame filter press to obtain plate-and-frame filter liquor;
3) Cooling the plate-and-frame filter pressing liquid obtained in the step 1) to 20-30 ℃;
4) Filtering the cooled plate-and-frame filter pressing liquid obtained in the step 3) by using an ultra-hydrophilic ceramic membrane;
5) Pre-filtering the concentrated solution of the super-hydrophilic ceramic membrane obtained in the step 4) in a plate-and-frame filter press together with the supernatant obtained in the step 1);
6) And (3) the super-hydrophilic ceramic membrane filtrate obtained in the step (4) enters an extraction process.
The method combines the ceramic membrane degreasing technology with the traditional sedimentation and plate-and-frame filter pressing method, obviously reduces the tar content in the m-phenylenediamine acidic hydrolysate, solves the problems of reduced extraction and distillation efficiency, even process interruption and pipeline blockage caused by overhigh tar content in the extraction and refining processes of resorcinol products, and increases the reuse water quantity. Not only reduces the running cost and improves the product quality and the recovery rate, but also reduces the discharge capacity, thereby being beneficial to environmental protection.
The acid hydrolysate in the step 1) is the acid hydrolysate which is dehydrated through flash evaporation after reaction, and the concentration of the sulfuric acid is 6-8%, the tar content is 600-1000 mg/L and the temperature is about 220 ℃. The tar content is usually within the range of tar content, and it is needless to say that the tar content can be reduced to 100mg/L or less by the method of the present invention if the tar content exceeds 1000 mg/L.
In order to improve the efficiency and stability of removing tar of the ceramic membrane, reduce the tar content and the temperature at the same time, in the step 1), the acid hydrolysate is firstly settled to remove the bulk tar and coke powder; in the step 2), removing large-particle carbon powder and a small amount of tar by using a plate-and-frame filter press; in the step 3), in order to improve the rejection rate of the ceramic membrane to tar, the temperature of the acidic hydrolysate before membrane feeding is further required to be reduced; in the step 4), tar in the acidic hydrolysate is removed by utilizing the high-precision degreasing performance of the super-hydrophilic ceramic membrane; feeding the concentrated solution obtained by concentrating the super-hydrophilic ceramic membrane in the step 5) into a plate-and-frame filter press, recycling large-particle tar and coke powder, and feeding the filtrate of the plate-and-frame filter press into the super-hydrophilic ceramic membrane again to remove tar; and 5) directly entering the super-hydrophilic ceramic membrane filtrate in the step 5) into the extraction process of the next working procedure.
In order to remove suspended matters such as large-particle tar oil drops and the like and prevent membrane channels from being blocked, in the step 2), the precision of the plate-and-frame filter press is 400-800 meshes.
In order to further improve the rejection rate of the ceramic membrane to tar, in the step 3), the filtrate of the plate-and-frame filter press is cooled to 20-25 ℃.
In order to achieve both the treatment efficiency and the effect, in the step 4), the operation pressure of the ultra-hydrophilic ceramic membrane filtration is 0.1-0.3 MPa, the membrane surface flow rate is 3-5 m/s, and the temperature is controlled at 20-25 ℃.
In order to better consider the treatment efficiency and effect, the pore diameter of the super-hydrophilic ceramic membrane in the step 4) is 2-50 nm, the porosity is 37-45%, and the material is ceramics such as alumina, zirconia, titania or silicon carbide.
In order to achieve both high tar removal and low product loss, in the step 4), the super-hydrophilic ceramic membrane is modified by adopting a solution of 3,5 diiodo-tyrosine or octanoic acid with the mass concentration of 1-3 percent. The ceramic membrane is fully soaked in 3,5 diiodo-amino acid or caprylic acid solution (50-90 ℃) with the mass concentration of 1-3 percent (13-15 hours), and then naturally dried at room temperature, thus finishing modification and obtaining the super-hydrophilic ceramic membrane.
In the step 5), when the concentration multiple of the super-hydrophilic ceramic membrane reaches 50-100, the concentrated solution of the super-hydrophilic ceramic membrane enters a plate-and-frame filter press to be prefiltered together with the supernatant obtained in the step 1).
A device for removing tar from m-phenylenediamine acidic hydrolysate comprises a settling tank, a plate-and-frame filter press, a heat exchanger, a ceramic membrane circulating pump and an ultra-hydrophilic ceramic membrane component which are sequentially communicated; the concentrated solution outlet of the super-hydrophilic ceramic membrane component is communicated with the feed inlet of the plate-and-frame filter press.
The technology not mentioned in the present invention refers to the prior art.
The method for removing tar in the m-phenylenediamine acidic hydrolysate combines the super-hydrophilic ceramic membrane tar removal technology with the traditional sedimentation and plate-and-frame filter pressing technology, utilizes the super-hydrophilic ceramic membrane to intercept dispersed tar at low temperature, fully combines the super-hydrophilic ceramic membrane with the sedimentation and removal bulk oil and carbon powder and the plate-and-frame technology to remove large-particle suspension oil and carbon powder, plays respective advantages and characteristics, effectively reduces the tar content in the m-phenylenediamine acidic hydrolysate, solves the problems of unsmooth extraction and distillation technology, equipment pipeline blockage and the like caused by the too high tar content, and greatly improves the production efficiency and the product quality. Compared with the existing simple active carbon tar removal process, the invention has the following advantages:
1) High-efficiency tar removal effect: besides low tar content, the activated carbon is easy to adsorb and saturate and generates frequent regeneration problems, thus influencing the normal production; the super-hydrophilic ceramic membrane is utilized to remove tar, molecular-level filtration is adopted, and besides the cross-flow technology is adopted to reduce membrane pollution, the oleophobic hydrophilicity of the super-hydrophilic ceramic membrane reduces the adsorption of tar on the membrane surface to the minimum, so that the high-flux operation of the ceramic membrane is ensured, the high retention rate of tar is ensured, and the practice proves that the tar content of filtrate of the super-hydrophilic ceramic membrane is reduced to below 100mg/L, and the normal operation of equipment is satisfied.
2) No interception of the product is generated: the active carbon is used for removing tar, and the active carbon has high surface adsorption performance, and the adsorption performance is not selective, so that not only can a trace amount of tar be adsorbed, but also organic matters in the active carbon can be adsorbed, thus the product yield is reduced, the tar is required to be extracted and removed in the prior art, but the problems of low extraction efficiency, influence on the product quality, blockage of a pipeline and the like are caused by the existence of the tar; the invention can separate tar and product with high efficiency, with little interception, to remove tar, to improve the quality and yield of product.
3) There is no limitation on the tar content of the treated raw material: as described in the above item 1), the activated carbon tar removal requires low tar content, otherwise it is easily saturated; the invention removes the coke oil drop and carbon powder with big particles by sedimentation and plate frame filter pressing, and the ceramic membrane can treat the fine granular tar and carbon powder dispersed in the hydrolysate without being limited by concentration.
4) No hazardous waste is generated: more importantly, the activated carbon generates a lot of waste activated carbon after being adsorbed and saturated, and the waste activated carbon with organic amine and phenol is harmful to the environment, needs special treatment, has high treatment cost and is easy to generate secondary pollution; the super-hydrophilic ceramic membrane filter has no generation of hazardous wastes, is environment-friendly, does not generate treatment cost of the hazardous wastes, and is economical and environment-friendly.
5) The use of the cooling measures increases the tar interception capability of the ceramic membrane, improves the quality of filtrate, has good guarantee effect on the quality of products and the stability of the process, and thus saves the operation cost for enterprises and brings economic benefit.
Drawings
FIG. 1 is a schematic diagram of a process flow for removing tar from an acidic m-phenylenediamine hydrolysate;
in the figure, 1, a settling tank, 2, a plate-and-frame filter press, 3, a heat exchanger, 4, a ceramic membrane circulating pump, 5, a ceramic membrane component, a, m-phenylenediamine acidic hydrolysate, b, settling supernatant, c, plate-and-frame filter press filtrate, d, low-temperature hydrolysate, e, super-hydrophilic ceramic membrane concentrated solution, f, super-hydrophilic ceramic membrane filtrate, g and plate-and-frame filter press residues.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples. The specific techniques and conditions are not specified in the examples, and are carried out according to techniques and conditions described in the literature in the art (for example, refer to Xu Naping et al, inorganic membrane separation techniques and applications, chemical industry Press, 2003) or according to the product specifications.
As shown in figure 1, the device for removing tar from m-phenylenediamine acidic hydrolysate comprises a settling tank 1, a plate-and-frame filter press 2, a heat exchanger 3, a ceramic membrane circulating pump 4 and a super-hydrophilic ceramic membrane assembly 5 which are sequentially communicated; the concentrated solution outlet of the super-hydrophilic ceramic membrane component 5 is communicated with the feed inlet of the plate-and-frame filter press 2.
Example 1
A method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Pouring the flash-evaporated m-phenylenediamine acidic hydrolysate a (with the temperature of 220 ℃ C., the sulfur content of 6.5 percent and the tar content of 650 mg/L) into a settling tank 1, and carrying out settling oil removal for 24 hours, wherein the temperature is reduced to 55 ℃ C., and the tar content in a supernatant fluid b is reduced to 380mg/L;
2) Pre-filtering the settled supernatant b by adopting a plate-and-frame filter press 2 with the precision of 800 meshes, wherein the temperature of plate-and-frame filter pressing liquid c after plate-and-frame filter pressing is 45 ℃, and the tar content is 320mg/L;
3) Continuously cooling the plate frame pressure filtrate c to 23 ℃ by using a heat exchanger 3, wherein the tar concentration is unchanged;
4) And conveying the acidic hydrolysate d cooled by the heat exchanger 3 to the super-hydrophilic ceramic membrane assembly 5 by using the ceramic membrane circulating pump 4, and filtering. The pore diameter of the super-hydrophilic ceramic membrane is 30nm, the porosity is 42%, the material is alumina, 3% of 3,5 diiodo-amino acid solution is adopted for soaking modification, the ceramic membrane is soaked in 3,5 diiodo-amino acid solution with the mass concentration of 3% (the temperature is 70-80 ℃) for 13 hours, then the ceramic membrane is naturally dried at room temperature, the modification is completed, the operating pressure of the ceramic membrane is 0.2MPa, the membrane surface flow rate is 4m/s, and the temperature is controlled at 20-25 ℃;
5) When the concentration multiple of the super-hydrophilic ceramic membrane is 50, feeding the concentrated solution e of the super-hydrophilic ceramic membrane into a plate-and-frame filter press 2, and removing large-particle oil drops together with the settling supernatant b;
6) The temperature of the super-hydrophilic ceramic membrane filtrate f is 20-25 ℃, the tar content is 83mg/L, and the super-hydrophilic ceramic membrane filtrate f enters an extraction process.
Example 2
A method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Pouring the flash-evaporated m-phenylenediamine acidic hydrolysate a (with the temperature of 220 ℃ and the sulfur content of 6.5 percent and the tar content of 1000 mg/L) into a settling tank 1, and performing settling oil removal for 24 hours, wherein the temperature is reduced to 55 ℃ and the tar content in a supernatant fluid b is reduced to 482mg/L;
2) Pre-filtering the settled supernatant b by adopting a plate-and-frame filter press 2 with the precision of 800 meshes, wherein the temperature of plate-and-frame filter pressing liquid c after plate-and-frame filter pressing is 45 ℃, and the tar content is 427mg/L;
3) Continuously cooling the plate frame pressure filtrate c to 23 ℃ by using a heat exchanger 3, wherein the tar concentration is unchanged;
4) Delivering the acidic hydrolysate d cooled by the heat exchanger 3 into a ceramic membrane circulating pump 4 provided with a super-hydrophilic ceramic membrane assembly 5 for filtering, wherein the aperture of the super-hydrophilic ceramic membrane is 30nm, the porosity is 42%, the material is alumina, 3% 3,5 diiodo-amino acid solution is adopted for soaking modification, the ceramic membrane is soaked in 3,5 diiodo-amino acid solution with the mass concentration of 3% (the temperature is 70-80 ℃) for 13 hours, then naturally dried at room temperature, the operation pressure of the ceramic membrane is 0.2MPa, the membrane surface flow rate is 4m/s, and the temperature is controlled at 20-25 ℃;
5) When the concentration multiple of the super-hydrophilic ceramic membrane is 50, feeding the concentrated solution e of the super-hydrophilic ceramic membrane into a plate-and-frame filter press 2, and removing large-particle oil drops together with the settling supernatant b;
6) The temperature of the super-hydrophilic ceramic membrane filtrate f is 20-25 ℃, the tar content is 79mg/L, and the super-hydrophilic ceramic membrane filtrate f enters an extraction process.
In order to prove the tar removal effect of the super-hydrophilic ceramic membrane, the common ceramic membrane is adopted to carry out filtration verification on the acidic hydrolysate under the same condition, and the result is as follows:
comparative example 1
A method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Pouring the flash-evaporated m-phenylenediamine acidic hydrolysate a (with the temperature of 220 ℃ C., the sulfur content of 6.5 percent and the tar content of 650 mg/L) into a settling tank 1, and carrying out settling oil removal for 24 hours, wherein the temperature is reduced to 55 ℃ C., and the tar content in a supernatant fluid b is reduced to 380mg/L;
2) Pre-filtering the settled supernatant b by adopting a plate-and-frame filter press 2 with the precision of 800 meshes, wherein the temperature of filtrate C after plate-and-frame filter pressing is 45 ℃, and the tar content is 320mg/L;
3) Continuously cooling the plate frame pressure filtrate c to 23 ℃ by using a heat exchanger 3, wherein the tar concentration is unchanged;
4) And conveying the acidic hydrolysate d cooled by the heat exchanger 3 into a ceramic membrane circulating pump 4 provided with a common ceramic membrane assembly 5 for filtering, wherein the common ceramic membrane has a pore diameter of 30nm and a porosity of 42%, and is made of alumina. The operating pressure of the ceramic membrane is 0.2MPa, the flow rate of the membrane surface is 4m/s, and the temperature is controlled at 20-25 ℃;
5) When the concentration multiple of the ceramic membrane is 50, the concentrated solution e of the ceramic membrane enters the plate-and-frame filter press 2 and large-particle oil drops are removed together with the settled supernatant b.
6) The temperature of the ceramic membrane filtrate f is 20-25 ℃, the tar content is 139mg/L, and the ceramic membrane filtrate f enters an extraction process.
It can be seen from this: the tar content in the filtrate of the super-hydrophilic ceramic membrane is obviously lower than that of the common ceramic membrane, so that the capability of the super-hydrophilic ceramic membrane for intercepting tar is proved to be obviously higher than that of the common ceramic membrane.
In order to prove that the use of the cooling measures can improve the retention rate of tar and thus improve the product quality, the experimental effect comparison is carried out on the acidic hydrolysate without cooling under the same condition by researching the adoption of the hydrophilic ceramic membrane. The results were as follows:
comparative example 2
A method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Pouring the flash-evaporated m-phenylenediamine acidic hydrolysate a (with the temperature of 220 ℃ C., the sulfur content of 6.5 percent and the tar content of 650 mg/L) into a settling tank 1, and carrying out settling oil removal for 24 hours, wherein the temperature is reduced to 55 ℃ C., and the tar content in a supernatant c is reduced to 380mg/L;
2) Pre-filtering the settled supernatant b by adopting a plate-and-frame filter press 2 with the precision of 800 meshes, wherein the temperature of filtrate C after plate-and-frame filter pressing is 45 ℃, and the tar content is 320mg/L;
3) And (3) conveying the acidic hydrolysate c subjected to plate-frame filter pressing into a ceramic membrane assembly 5 provided with a super-hydrophilic ceramic membrane, filtering, wherein the aperture of the super-hydrophilic ceramic membrane is 30nm, the porosity is 42%, the material is alumina, soaking and modifying the super-hydrophilic ceramic membrane by adopting 3% of 3,5 diiodo-amino acid solution, soaking the ceramic membrane in the 3,5 diiodo-amino acid solution with the mass concentration of 3% (the temperature is 70-80 ℃) for 13h, and naturally airing the ceramic membrane at room temperature to finish modification. The operating pressure of the ceramic membrane is 0.2MPa, the flow rate of the membrane surface is 4m/s, and the temperature is controlled at 40-45 ℃;
4) When the concentration multiple of the ceramic membrane is 50, the concentrated solution e of the ceramic membrane enters the plate-and-frame filter press 2 and large-particle oil drops are removed together with the settled supernatant b.
5) The temperature of the ceramic membrane filtrate f is 40-48 ℃, the tar content is 215mg/L, and the ceramic membrane filtrate f enters an extraction process.
It can be seen from this: the temperature plays a very important key role in reducing the tar content in the hydrophilic ceramic membrane filtrate. Therefore, the temperature must be lowered for filtration.
In order to prove the influence of the implementation of the process on the improvement of the retention rate of tar and the improvement of the product quality and recovery rate, the experiment effect comparison is carried out under the same condition by researching the prior process of extraction and then adsorption. The results were as follows:
comparative example 3
A method for removing tar from m-phenylenediamine acidic hydrolysate comprises the following steps:
1) Pouring the flash-evaporated m-phenylenediamine acidic hydrolysate a (with the temperature of 220 ℃ C., the sulfur content of 6.5 percent and the tar content of 650 mg/L) into a settling tank 1, and carrying out settling oil removal for 24 hours, wherein the temperature is reduced to 55 ℃ C., and the tar content in a supernatant fluid b is reduced to 380mg/L;
2) Pre-filtering the settled supernatant b by adopting a plate-and-frame filter press 2 with the precision of 800 meshes, wherein the temperature of filtrate C after plate-and-frame filter pressing is 45 ℃, and the tar content is 320mg/L;
3) And (3) extracting part of the acidic hydrolysate c subjected to plate and frame filter pressing firstly, then adsorbing tar in a raffinate phase by using active carbon, and then distilling the extract phase to obtain crude phenol, wherein the waste water in the raffinate phase is subjected to active carbon adsorption for 2 times. And the other part is subjected to the ceramic membrane filtration process after temperature reduction in the embodiment 1, and then the filtrate of the ceramic membrane is extracted and distilled to obtain a crude phenol product. Almost no tar is produced in the waste water of the raffinate phase, and the waste water can be directly recycled. The results of the two processes are shown in the following table.
Table 1 comparison of results of the adsorption-first extraction process and the ceramic membrane filtration-last extraction process
In table 1, the extraction and adsorption process is identical to the extraction process in the ceramic membrane filtration and then extraction process, and ethyl acetate countercurrent extraction is adopted.
As can be seen from table 1: if the m-phenylenediamine acidic hydrolysate after flash evaporation, sedimentation and plate-frame filter pressing is extracted first and then the tar in the raffinate is adsorbed by the activated carbon, the product content obtained by the method is about 9% lower than that obtained by the extraction process after ceramic membrane filtration, the recovery rate of phenol is about 11% lower, and the waste water serving as the raffinate can only be used for 2 times in the process of extracting and then adsorbing before the extraction process after the ceramic membrane filtration, but the method is not limited in the process of extracting after the ceramic membrane filtration. It is thus evident that: the process has great advantages over the extraction-then-adsorption process.
Claims (6)
1. A method for removing tar from m-phenylenediamine acidic hydrolysate is characterized by comprising the following steps: the method comprises the following steps:
1) Settling and deoiling the m-phenylenediamine acidic hydrolysate;
2) Pre-filtering the supernatant obtained in the step 1) by adopting a plate-and-frame filter press to obtain plate-and-frame filter liquor;
3) Cooling the plate and frame filter pressing liquid obtained in the step 2) to 20-30 ℃;
4) Filtering the cooled plate-and-frame filter pressing liquid obtained in the step 3) by using an ultra-hydrophilic ceramic membrane;
5) Pre-filtering the concentrated solution of the super-hydrophilic ceramic membrane obtained in the step 4) in a plate-and-frame filter press together with the supernatant obtained in the step 1);
6) The super-hydrophilic ceramic membrane filtrate obtained in the step 4) enters an extraction procedure;
in the step 4), the pore diameter of the super-hydrophilic ceramic membrane is 2-50 nm, the porosity is 37-45%, and the super-hydrophilic ceramic membrane is made of alumina, zirconia, titanium oxide or silicon carbide ceramic;
in the step 4), the super-hydrophilic ceramic membrane is modified by adopting 3,5 diiodo-aqua ammonia solution with the mass concentration of 1-3%; the modification method comprises the following steps: soaking the ceramic membrane in a 3,5 diiodo-amino acid solution with the mass concentration of 1-3% and the temperature of 50-90 ℃ for 13-15 h, and naturally airing at room temperature to finish modification, thereby obtaining the super-hydrophilic ceramic membrane.
2. The method for removing tar from m-phenylenediamine acidic hydrolysate according to claim 1, wherein the method comprises the following steps: in the step 1), the acidic hydrolysate is dehydrated by flash evaporation after reaction, the concentration of sulfuric acid is 6-8%, the tar content is 600-1000 mg/L, and the temperature is 200-240 ℃.
3. The method for removing tar from m-phenylenediamine acidic hydrolysate according to claim 1 or 2, wherein the method comprises the following steps: in the step 2), the precision of the plate-and-frame filter press is 400-800 meshes.
4. The method for removing tar from the acidic hydrolysate of m-phenylenediamine according to claim 1 or 2, characterized by comprising the steps of: in the step 3), the filtrate of the plate-and-frame filter press is cooled to 20-25 ℃.
5. The method for removing tar from the acidic hydrolysate of m-phenylenediamine according to claim 1 or 2, characterized by comprising the steps of: in the step 4), the operation pressure of the ultra-hydrophilic ceramic membrane filtration is 0.1-0.3 MPa, the membrane surface flow rate is 3-5 m/s, and the temperature is controlled at 20-25 ℃.
6. The method for removing tar from the acidic hydrolysate of m-phenylenediamine according to claim 1 or 2, characterized by comprising the steps of: in the step 5), when the concentration multiple of the super-hydrophilic ceramic membrane reaches 50-100, the concentrated solution of the super-hydrophilic ceramic membrane enters a plate-and-frame filter press to be prefiltered together with the supernatant obtained in the step 1).
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