CN109694319A - A kind of device and method for handling the solid waste containing organic acid - Google Patents
A kind of device and method for handling the solid waste containing organic acid Download PDFInfo
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- CN109694319A CN109694319A CN201710990496.5A CN201710990496A CN109694319A CN 109694319 A CN109694319 A CN 109694319A CN 201710990496 A CN201710990496 A CN 201710990496A CN 109694319 A CN109694319 A CN 109694319A
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- organic acid
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- sublimation
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- 150000007524 organic acids Chemical class 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002910 solid waste Substances 0.000 title claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000011343 solid material Substances 0.000 claims abstract description 42
- 238000004821 distillation Methods 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 26
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 23
- 238000012545 processing Methods 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims description 83
- 238000000859 sublimation Methods 0.000 claims description 69
- 230000008022 sublimation Effects 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 83
- 230000003647 oxidation Effects 0.000 abstract description 22
- 238000007254 oxidation reaction Methods 0.000 abstract description 22
- 238000007781 pre-processing Methods 0.000 abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract 1
- 239000008096 xylene Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 239000005711 Benzoic acid Substances 0.000 description 7
- 235000010233 benzoic acid Nutrition 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910020632 Co Mn Inorganic materials 0.000 description 2
- 229910020678 Co—Mn Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NMQPIBPZSLMCFI-UHFFFAOYSA-N 2-(4-methylphenyl)acetamide Chemical compound CC1=CC=C(CC(N)=O)C=C1 NMQPIBPZSLMCFI-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009288 screen filtration Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention relates to a kind of device and method for handling the solid waste containing organic acid.The present invention passes through while using the solid material heater and decarboxylic reaction device of specific structure, so that content is higher in the solid waste containing organic acid and the organic acid that is easily isolated directly is recycled by distillation mode first, the preprocessing process of solid waste before catalytic decarboxylation is optimized.After distillation is handled, isolated mixed organic acid component is difficult in the component that distils, hydrocarbon product is converted by catalytic decarboxylation.The present invention is not only that solid residue and gas each provide channel, and improve capacity usage ratio.Recycling, the minimizing processing of the solid waste containing organic acid can be realized through the invention, and processing cost is low, especially suitable for the processing of residue in p xylene oxidation terephthalic acid process, has significant economic benefit.
Description
Technical field
The invention belongs to the processing technology fields of solid waste, and in particular to a kind of solid for handling containing organic acid
The device and method of waste.
Background technique
The organic acids such as terephthalic acid (TPA) are textile industry and the important organic synthesis monomer of plastics industry.Due to polyester industrial
Promotion, organic acid demand rapid growth.In contrast, the production of terephthalic acid (TPA) is asked with the processing of a large amount of solid waste
Topic, attracts extensive attention.In actual production, solid waste mostly uses incineration method and burial method to handle, and also has Some Enterprises simple
Sewage treatment plant directly is discharged into waste water after single recycling metallic catalyst.These processing methods have recycling in waste residue
It is caused serious environmental pollution while the component of value.
More organic acid and a small amount of metal are usually contained in the solid waste generated in organic acid production process
Catalyst, recycling value with higher.By taking the residue of by-product in purified terephthalic (PTA) production as an example, to two
Aromatic acid in the rinsing residue precipitated in the oxidation residua and PTA process units sewage of toluene oxidation synthesis PTA byproduct in process
Content is typically up to 90% or more, and developing and using the organic acid in PTA residue becomes the hot spot of solid waste processing.
CN1126730C discloses a kind of process for separation and purification of PTA residue.By solid terephthalic acid waste material be put by
In the nitration mixture of sulfuric acid and nitric acid composition, slurry is obtained into filter cake with filter screen filtration under negative pressure, is washed in washing pool with desalination
It washs and obtains terephthalic acid (TPA) after drying.CN1012954B discloses a kind of separation method of PTA residue.Oxidation residua is carried out
Then washing process carries out selective reaction under high temperature, salt of weak acid existence condition, make terephthalic acid (TPA) and M-phthalic acid point
From.It is stripped again with solvent, realizes terephthalic acid (TPA), M-phthalic acid separation.CN101139277 discloses a kind of using high
The method that warm water is washed is come the method that recycles terephthalic acid (TPA) in PTA residue.CN200810062425 discloses one kind and passes through complexing
Isolated method is crystallized, terephthalic acid (TPA), etc. can be recycled from coloured PTA residue using this method.Above-mentioned PTA residue
Separation and recovery is using the physics and chemical property difference between different component, using distillation, extraction, precipitating, crystallization, esterification, charing
The methods of purification one-component or realize PTA residue resource utilization.However the materialization in PTA residue between the binary acid of benzene
Property is very much like, and it is higher that more difficulty, separation costs are separated between component.On the other hand, the ingredient of different PTA residues exists
Difference, recycling gained terephthalate product quality are usually unable to satisfy strict demand of the polyester industrial to monomer.
CN103467237A discloses the method for another PTA residue as resources, i.e., is catalyzed by terephthalic acid residue
Aromatic acid in residue is the aromatic hydrocarbons such as benzene, toluene by catalytic decarboxylation by the method that decarboxylation prepares aromatic hydrocarbons.Catalytic decarboxylation will
The higher benzene dibasic acid component of separating difficulty is uniformly converted into the aromatic product being easily isolated, reduce treatment process energy consumption and
Cost.The difficult point that the invention is implemented is the pretreatment of solid waste, and the method for handling solid waste is to improve catalysis to take off
The key point of carboxylic processing route competitiveness.The pretreated method of PTA residue is conveyed and is heated in material in CN103467237A
Separate section lacks reasonable design, fails the advantage for giving full play to catalytic decarboxylation processing solid waste.
Therefore, presently, there are the problem of be badly in need of researching and developing a kind of achievable recycling, minimizing contains for handling
The device and method of the solid waste of organic acid.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide one kind to contain for handling
The device and method of the solid waste of machine acid.The present invention passes through while using the solid material heater of specific structure and decarboxylation
Reactor, so that content is higher in the solid waste containing organic acid and the organic acid that is easily isolated is straight by distillation mode first
Recycling is connect, the preprocessing process of solid waste before catalytic decarboxylation is optimized.After distillation is handled, it is difficult in the component that distils
Isolated mixed organic acid component is converted into hydrocarbon product by catalytic decarboxylation.In addition, the present invention pass through it is residual to non-sublimation solid
Co-Mn metal etc. can be obtained in the separating treatment of slag, and resource utilization is high.
For this purpose, first aspect present invention provides a kind of for handling the device of the solid waste containing organic acid, packet
It includes sequentially connected
The heating unit of sublimation separation is carried out to the solid waste containing organic acid,
The anti-of catalytic decarboxylation is carried out to isolated mixed organic acid component is difficult to from the distillation component that heating unit obtains
Unit is answered,
The separative unit that the hydrocarbon product obtained from reaction member is separated and recovered.
According to the present invention, the heating unit includes at least one solid material heater, for conveying, heating and distil
Solid waste containing organic acid.The solid material heater is divided into closely knit conveying section and heating sublimation along Flow of Goods and Materials direction
Section.The heating sublimation section includes at least one sublimation unit.
According to the present invention, the solid material heater includes set on the feed end of closely knit conveying section and set on heating sublimation
The discharge end of section.Feed end in order to ensure the solid waste containing organic acid in solid material heater does not distil, to reach
The purpose that air-isolation enters is squeezed by solid waste, so that distillation carries out under conditions of anaerobic or anoxic, preferably
The discharge end is 50-550 DEG C higher than the temperature of the feed end.
The present invention only conveys material without heating using closely knit section of design, in solid material heater feed end, and utilization is close
Real section solid material squeezes air-isolation, is the key that guarantee that distillation operates under anaerobic state.
According to the present invention, the heating sublimation section is equipped with heating tube, and the discharge end is equipped with expanding reach.It is true by expanding reach
Having protected the solid residue not distilled will not be less easily entrained by into reaction member.It is preferred that the sectional area of the expanding reach adds with described
The ratio between sectional area of heat pipe is (1-100): 1.The solid residue not distilled is separated and recovered it is preferred that the expanding reach is equipped with
Solid residue outlet, the solid residue not distilled can be adopted and be further separated recycling with the conventional methods in the field, realization
Minimizing and innoxious.
The present invention is designed using expanding reach, and exporting setting expanding reach in heating sublimation section reduces gas linear velocity, entrainment
Solid is separated from gas component under the effect of gravity, is the key that reduce solid entrainment in gas component.
According to the present invention, the solid material heater preferably passes through screw rod transmission by screw rod or Belt Conveying material
Material.
According to the present invention, when containing more than two solid material heaters in the heating unit, the solids
Expect that the connection type between heater is serial or parallel connection.
According to the present invention, the heating medium in the heating unit is selected from one of steam, flue gas, conduction oil and fused salt
Or a variety of, preferably flue gas.Preferably, the flow direction of the heating medium in the heating unit is identical as Flow of Goods and Materials direction or phase
Instead, preferably on the contrary.
Fig. 1 shows the structural representation of the solid material heater in some preferred embodiments according to the present invention
Figure.Solid waste containing organic acid enters in solid material heater from the solid waste entrance 1 containing organic acid first.So
Use screw rod by the solid waste containing organic acid through closely knit conveying section 2 (main function is conveying material) and heating sublimation section afterwards
After the processing of 3 (main function is heating sublimation material), it is straight that sublimation gases pass through the sublimation gases outlet 7 being set on expanding reach 5
It takes back receipts or enters decarboxylic reaction device, the solid residue not distilled passes through the solid residue outlet 6 not distilled being set on expanding reach 5
Into series connection with it or solid material heater in parallel or enter residue separator.Closely knit conveying section 2 is equipped with feed end 21, adds
Heat sublimation section 3 is equipped with discharge end 31, and discharge end 31 is 50-550 DEG C higher than the temperature of feed end 21.Heating sublimation section 3 is equipped with heating
Pipe 4 heats heating tube 4 using heating medium.Heating medium entrance 32 and heating medium outlet 33 are respectively arranged on
The both ends of heating sublimation section 3.The flow direction of heating medium is contrary with Flow of Goods and Materials.(diameter of section is the sectional area of expanding reach 5
d1) with sectional area (the diameter of section d of heating tube 42) the ratio between be (1-100): 1.
According to the present invention, the reaction member contains at least one decarboxylic reaction device, by enter reaction member from heating
It is difficult to isolated mixed organic acid component in the distillation component obtained in unit and carries out catalytic decarboxylation processing, obtains hydrocarbon product.
The decarboxylic reaction device is selected from one of fixed bed reactors, fluidized-bed reactor and moving-burden bed reactor or a variety of, preferably
For fixed bed reactors.Preferably, when containing more than two decarboxylic reaction devices in the reaction member, the decarboxylic reaction
Connection type between device is serial or parallel connection；The method of operation between the decarboxylic reaction device is that one to open one standby or open more more
It is standby.
According to the present invention, in the decarboxylic reaction device for catalytic decarboxylation catalyst activity component be selected from calcium, magnesium, zinc,
One of metal oxide of iron and manganese is a variety of, and carrier is selected from the oxide of silicon or the oxide of aluminium.
Preferably, the partial pressure that inert gas adjusts organic acid composition can be passed through in the decarboxylic reaction device.
According to the present invention, the outlet temperature of adverse effect caused by endothermic heat of reaction in order to prevent, the heating unit is not low
In the reaction temperature of the reaction member, the reaction temperature of the reaction member is 350-550 DEG C；It is preferred that the heating unit
The difference of outlet temperature and the reaction temperature of the reaction member is 0-200 DEG C.
Fig. 2 shows anti-comprising solid material heater and decarboxylation in some preferred embodiments according to the present invention
Answer the schematic diagram of the device of device.Solid waste containing organic acid enters from the solid waste entrance 1 containing organic acid solid first
In body material heater.Then after the processing of material conveying sublimator 8, obtained distillation component 9 is entered into decarboxylic reaction device
11 carry out decarboxylic reaction, and the obtained solid residue 10 not distilled is entered residue separator and is handled.Finally, will be from decarboxylic reaction
The hydrocarbon component 12 that device 11 obtains enters separative unit and handles.
According to the present invention, the solid waste containing organic acid is preferably in the organic acids production process such as terephthalic acid (TPA)
Oxidation residua, rinsing residue of generation etc. are rich in the solid waste of organic acid.
According to the present invention, described device further includes fuel element.For the high-efficiency comprehensive utilization of energy in realization device, institute
Fuel element is stated to the heating unit and reaction member heat supply, the reaction member is to the separative unit heat supply.
Second aspect of the present invention provides a kind of solid of the processing of described device according to a first aspect of the present invention containing organic acid
The method of waste comprising following steps:
A, after the processing of sublimation separation at least once of the heated unit of solid waste containing organic acid, by the component that distils
In segregative organic acid composition directly as Product recycling, be difficult to isolated mixed organic acid component in the component that will distil and enter
Reaction member separates and recovers the solid residue not distilled；
B is reacted isolated mixed organic acid group lease making catalytic decarboxylation is difficult in the distillation component for entering reaction member, is obtained
To hydrocarbon product；
C separates and recovers the hydrocarbon product in separative unit.
According to the method for the present invention, using heating medium that the heat generated in fuel element supply heating unit and reaction is single
Member；Heating medium supplies separative unit after reaction member absorbs heat.Preferably, more than two when containing in heating unit
When sublimation unit, using heating medium by the heat generated in fuel element for giving an adjacent sublimation unit of reaction member
In, heating medium successively supplies adjacent thereto upper one along the method opposite with Flow of Goods and Materials after the sublimation unit absorbs heat
A sublimation unit.By the step heat-supplying mode in heating unit, the high-efficiency comprehensive utilization to energy in device is realized.
According to the method for the present invention, in step, the heating unit includes at least one solid material heater, described
Solid material heater is divided into closely knit conveying section and heating sublimation section along Flow of Goods and Materials direction, and the heating sublimation section includes at least
One sublimation unit.The solid material heater includes set on the feed end of closely knit conveying section and going out set on heating sublimation section
Expect end, the discharge end is 50-550 DEG C higher than the temperature of the feed end.
According to the method for the present invention, isolated mixed organic acid component is difficult in the component that distils to enter from the outlet of heating unit
Reaction member, the reaction temperature of the reaction member are 350-550 DEG C；It is preferred that the outlet temperature of the heating unit and described anti-
The difference for answering the reaction temperature of unit is 0-200 DEG C.
According to the method for the present invention, in step, the heated cell processing organic acid distillation of solid waste containing organic acid
Separation.The sublimation separation is primary distillation or distils step by step that this depends on the group of organic acid in the solid waste containing organic acid
At.Fig. 3 is the flow diagram of the method for solid waste of the present invention processing containing organic acid.In Fig. 3, consolidating containing organic acid
After the heating of body waste, sublimation separation (primary distillation) obtains organic acid (the distillation component compared with small molecule in sublimation unit 1
1)；The solid waste not distilled enters sublimation unit 2, and sublimation separation (secondary distillation) obtains larger point in sublimation unit 2
The organic acid (distillation component 2) of son；And so on, the solid waste not distilled enters sublimation unit N, in sublimation unit N
Sublimation separation (n times distillation) is elevated component N, into reaction member progress catalytic decarboxylation, the solid waste not distilled (Gu
Body residue) individually carry out separating treatment.The hydrocarbon product obtained from reaction member enters separative unit, through N number of in separative unit
The effect of separator respectively is isolated by component 1 to component N.Energy in the method for the present invention is supplied using step heat-supplying mode.?
In Fig. 3, the mixture (also may include isolated several combustible gas components from separative unit) of fuel and air is firing
It burns burning in unit and generates the heating medium containing heat, respectively to reaction member and sublimation unit N heat supply.Heating medium is anti-
To separative unit heat supply after answering unit to absorb heat, and heating medium is absorbed after heat in sublimation unit N to sublimation unit N-1
Heat supply, heating medium are absorbed after heat in sublimation unit N-1 to sublimation unit N-2 heat supply, and so on, heating medium is rising
To 1 heat supply of sublimation unit after absorption heat in magnificent unit 2.
According to the method for the present invention, the fuel is selected from one of natural gas, coal, biomass fuel, fuel oil or a variety of,
It can be using the fuel gas generated in the method for the present invention.
According to the method for the present invention, in step C, it is de- that isolated mixed organic acid group lease making catalysis is difficult in the component that will distil
The hydrocarbon product that carboxylic reacts enters separative unit and is separated and recovered, and the isolated mode can be conventional using this field
Method, such as selected from one of rectifying, UF membrane and absorption or a variety of, preferably rectifying.Pass through isolated regulation purity
Product.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention proposes reasonable resource utilization side for the Characteristics of Chemical Constituents of the solid waste containing organic acid
Method will be in distillation component by the way that the solid material heater and decarboxylic reaction device containing sublimation unit of specific structure is used in combination
Content it is higher and be easily isolated organic acid distillation after directly recycle, will distillation component in be difficult to isolated mixed organic acid
Component is converted into hydrocarbon product by catalytic decarboxylation, and also separates in the solid residue never to distil and obtain Co-Mn metal etc.,
Resource utilization is high, particularly suitable for the solid waste containing organic acid obtained in processing terephthalic acid (TPA) (PTA) production process
Object；
(2) present invention is handled by the primary distillation to the solid waste containing organic acid or step by step distillation, is optimized and is urged
The preprocessing process of solid waste before change decarboxylation；
(3) present invention is in solid material heater by designing closely knit section and heating sublimation section, can prevent air into
Enter in solid material heater, expanding reach is designed by the discharge end in solid material heater, it is ensured that the solid not distilled is residual
Slag will not be less easily entrained by into decarboxylic reaction device.
Detailed description of the invention
It is next with reference to the accompanying drawing that invention is further described in detail.
Fig. 1 is the structural schematic diagram of solid material heater of the invention；The meaning of appended drawing reference is as follows in figure: 1- contains
The solid waste entrance of machine acid；The closely knit conveying section 2-；3- heating sublimation section；4- heating tube；5- expanding reach；What 6- did not distilled consolidates
Body solid discharge；The outlet of 7- sublimation gases；21- feed end；31- discharging section；32- is for heater gas inlet port；33- goes out for hot gas
Mouthful；
Fig. 2 is the schematic diagram of device of the present invention comprising solid material heater and decarboxylic reaction device；Appended drawing reference in figure
Meaning it is as follows: solid waste entrance of the 1- containing organic acid；8- logistics delivery sublimator；9- sublimation gases；What 10- did not distilled
Solid residue；11- decarboxylic reaction device；12- enters the hydrocarbon product of separative unit；
Fig. 3 is the flow diagram of the method for the solid waste of processing of the invention containing organic acid, and solid line indicates in figure
Material conveying direction, dotted line indicate energy supply direction；
Fig. 4 is the flow diagram of the PTA oxidation residua processing method of the embodiment of the present invention 1, and solid line indicates material in figure
Conveying direction, dotted line indicate energy supply direction；
Fig. 5 is the flow diagram of the PTA rinsing residue processing method of the embodiment of the present invention 2, and solid line indicates material in figure
Conveying direction, dotted line indicate energy supply direction.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment and attached drawing, the present invention will be described in detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention.
Embodiment
Embodiment 1
The present embodiment chooses the oxidation residua generated in certain PTA production process as raw material, PTA oxidation residua typical case composition
As shown in table 1.
1 PTA oxidation residua typical composition of table
| Substance | Mass percent |
| Terephthalic acid (TPA) | 30.3% |
| M-phthalic acid | 35.4% |
| Phthalic acid | 0.66% |
| Benzoic acid | 31.5% |
| P-methylbenzoic acid | 1.07% |
| P-tolyl aldehyde | 0.32% |
| Solid insoluble | 0.75% |
The present embodiment handles the method flow diagram of PTA oxidation residua as shown in figure 4, specific processing method is as follows:
Heating unit (distils) step by step: due to containing the up to benzoic acid of 31.5wt%, and benzoic acid in PTA oxidation residua
Sublimation temperature is lower to be easily isolated purification, to such residuum feedstocks using second level distil, using two solid material heaters (Gu
The structure of body material heater is as shown in Figure 1, wherein first solid material heater and second solid material heater
Sectional area (the diameter of section d of expanding reach 51) with sectional area (the diameter of section d of heating tube 42) the ratio between be respectively 60:1 and
40:1) connect.The first order distils feeding temperature as room temperature (20 DEG C), and 1 outlet temperature of sublimation unit is 270 DEG C, defeated using screw rod
It send, for separating the benzoic acid in oxidation residua.Remaining solid material is sent into second solid material after the first order is distilled
Heater distillation, 2 outlet temperature of sublimation unit is 510 DEG C, using screw rod transmission.Second solid material heater distillation gained
Gas component enters reaction member decarboxylation, and the component that do not distil enters residue separator.
Reaction, separative unit: being made of two fixed bed reactors, takes one to open one and switches for mode convenient for catalyst,
Reaction temperature is 500 DEG C, synthesis under normal pressure.Zinc oxide, calcium oxide are chosen for active component, using aluminium oxide as carrier.Zinc oxide matter
Measuring percentage is 30%, and calcium oxide mass percent is 5%, remaining for carrier and binder (for example, silica solution, Aluminum sol or
Boehmite etc.).The mass space velocity of reactant is 0.2h-1.Liquid phase component successively enters reactor outlet product after cooling
Separator 1 and the isolated aromatic hydrocarbon product of separator 2 (i.e. benzene, toluene and biphenyl).
Fuel element: selection natural gas is fuel, and the flue gas generated using its burning is as heating medium.Burning gained is high
Warm flue gas (being higher than 700 DEG C) is first to reaction member and second level sublimation unit (i.e. sublimation unit 2) heat supply.Reaction member and second
Grade sublimation unit (i.e. sublimation unit 2) takes the flue gas after heat to supply to first order sublimation unit (i.e. sublimation unit 1) and separative unit
Heat, the low-temperature flue gas after heat supply are used for pre-heating fuel natural gas and air.
It is as follows using the present invention processing practical acquisition product of 1 ton of PTA oxidation residua: to be obtained about by sublimation separation step by step
0.315 ton of benzoic acid and 0.0075 ton of solid product containing metallic element, by catalytic decarboxylation obtain about 0.381 ton of benzene,
0.0063 ton of toluene and 0.0064 ton of biphenyl.In the case where the value for not calculating recycling metal, PTA oxidation residua per ton can be handled
It obtains value of the product and amounts to 5000 yuan or more.
Embodiment 2
The present embodiment chooses the rinsing residue generated in certain PTA production process as raw material, PTA rinsing residue typical case composition
Shown in table 2.
2 PTA rinsing residue typical composition of table
The present embodiment handles the method flow diagram of PTA rinsing residue as shown in figure 5, specific processing method is as follows:
Heating unit (distils) step by step: benzoic acid content is lower in PTA rinsing residue, uses single-stage to PTA rinsing residue
Distillation, (as shown in Figure 1, wherein sectional area (the diameter of section d of expanding reach 5 using a solid material heater1) and plus
Sectional area (the diameter of section d of heat pipe 42) the ratio between be 30:1) heating sublimation.Material is added with (20 DEG C) feeding solid materials of room temperature
Hot device distillation, outlet temperature is 530 DEG C, using screw rod transmission.Distillation gained gas component enters reaction member decarboxylation, does not distil
Component enters residue separator.
Reaction, separative unit: forming one by two fixed bed reactors and open one for production model, and reaction temperature is 515 DEG C,
Synthesis under normal pressure.Zinc oxide, magnesia are chosen for active component, using aluminium oxide as carrier.Zinc oxide mass percent is 30%, oxygen
Changing magnesium mass percent is 5%, remaining is carrier and binder.The mass space velocity of reactant is 0.4h-1.Reactor outlet product
Liquid phase component successively enters separator 1 and the isolated aromatic hydrocarbon product of separator 2 (i.e. benzene, toluene and biphenyl) after cooling.
Fuel element: selection natural gas is fuel, and the flue gas generated using its burning is as heating medium.Burning gained is high
Warm flue gas (being higher than 700 DEG C) is first to reaction member and sublimation unit heat supply.Reaction member and sublimation unit take the flue gas after heat to
Separative unit heat supply, the low-temperature flue gas after heat supply is for preheating natural gas and air.
It is as follows using the present invention processing practical acquisition product of 1 ton of PTA rinsing residue: about 0.0117 ton of consolidating containing metallic element
Body product obtains about 0.44 ton of benzene, 0.096 ton of toluene and 0.01 ton of biphenyl by catalytic decarboxylation.Do not calculate the valence of recycling metal
In the case where value, PTA oxidation residua per ton can handle to obtain 3000 yuan of value of the product total or more.
Comparative example 1
It is raw material that the present embodiment, which chooses the PTA oxidation residua in embodiment 1, and the present embodiment handles the side of PTA oxidation residua
Method with embodiment 1, the difference is that, solid material heater does not set closely knit conveying section.
The solid material heater for being not provided with closely knit conveying section exists as following drawbacks in actual use: for separation and recovery
Benzoic acid in PTA oxidation residua, first order distillation outlet temperature need to usually reach 250 DEG C or more.It distils and heats into the second level
When device, due to the sublimation temperature of feeding temperature constituent part close in residue, into heater rear portion, grouping decilitre China causes to add
Hot device can not completely cut off air completely.Since solid waste according to the present invention has certain corrosivity, longtime running will
Equipment leakproofness is caused to be deteriorated, the heater for being not provided with closely knit conveying section may cause material and leak and not can guarantee distillation in nothing
(organic acid oxidation that will lead in residue after air enters solid material heater causes damages) is operated under oxygen condition, more
Serious person may influence equipment normal operation.
Comparative example 2
It is raw material that the present embodiment, which chooses the PTA oxidation residua in embodiment 1, and the present embodiment handles the side of PTA oxidation residua
Method with embodiment 1, the difference is that, solid material heater is not provided with expanding reach.
The solid material heater for being not provided with expanding reach exists as following drawbacks in actual use: leading in PTA oxidation residua
Often contain a certain amount of metallic catalyst, is partially entrained in gas component after distillation is handled, finally together with gas component
Into reaction member.Since metallic catalyst exists with fine powder form solid waste according to the present invention after distilling, letter
Single gas solid separation can not completely remove.Metallic catalyst fine powder in PTA residue gradually accumulates after entering reaction member, attachment
It will lead to deacidification efficiency decline on deacidifying catalyst bed, more serious person may cause reactor plugs influence device and normally transport
Turn.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (11)
1. a kind of for handling the device of the solid waste containing organic acid comprising sequentially connected
The heating unit of sublimation separation is carried out to the solid waste containing organic acid,
To the reaction list for being difficult to isolated mixed organic acid component progress catalytic decarboxylation from the distillation component that heating unit obtains
Member,
The separative unit that the hydrocarbon product obtained from reaction member is separated and recovered；
The heating unit includes at least one solid material heater, and the solid material heater is along Flow of Goods and Materials direction point
For closely knit conveying section and heating sublimation section, the heating sublimation section includes at least one sublimation unit.
2. the apparatus according to claim 1, which is characterized in that the solid material heater includes to be set to closely knit conveying section
Feed end and discharge end set on heating sublimation section；It is preferred that the discharge end is 50-550 DEG C higher than the temperature of the feed end.
3. device according to claim 1 or 2, which is characterized in that the heating sublimation section is equipped with heating tube, the discharging
End is equipped with expanding reach, and the ratio between the sectional area of the expanding reach and the sectional area of the heating tube are (1-100): 1；It is preferred that the expansion
Big section is equipped with the solid residue separated and recovered to the solid residue not distilled and exports.
4. device described in any one of -3 according to claim 1, which is characterized in that the solid material heater passes through spiral shell
Bar or Belt Conveying material.
5. device described in any one of -4 according to claim 1, which is characterized in that there are two containing in the heating unit
When the above solid material heater, the connection type between the solid material heater is serial or parallel connection.
6. device described in any one of -5 according to claim 1, which is characterized in that the heating medium in the heating unit
Selected from one of steam, flue gas, conduction oil and fused salt or a variety of, preferably flue gas；
Preferably, the flow direction of the heating medium in the heating unit is identical as Flow of Goods and Materials direction or rather, it is preferred to opposite.
7. device described in any one of -6 according to claim 1, which is characterized in that the reaction member contains at least one
Decarboxylic reaction device；The decarboxylic reaction device is selected from one of fixed bed reactors, fluidized-bed reactor and moving-burden bed reactor
Or a variety of, preferably fixed bed reactors；
Preferably, the company when containing more than two decarboxylic reaction devices in the reaction member, between the decarboxylic reaction device
Connecing mode is serial or parallel connection.
8. device according to any one of claims 1-7, which is characterized in that the outlet temperature of the heating unit is not
Lower than the reaction temperature of the reaction member, the reaction temperature of the reaction member is 350-550 DEG C；It is preferred that the heating unit
Outlet temperature and the reaction member reaction temperature difference be 0-200 DEG C.
9. device described in any one of -8 according to claim 1, which is characterized in that described device further includes fuel element,
The fuel element is to the heating unit and reaction member heat supply, and the reaction member is to the separative unit heat supply.
10. a kind of method of solid waste of the processing of any one of -9 described devices according to claim 1 containing organic acid,
Include the following steps:
A will be easy in distillation component after the processing of sublimation separation at least once of the heated unit of solid waste containing organic acid
Isolated organic acid composition enters reaction directly as Product recycling, by isolated mixed organic acid component is difficult in distillation component
Unit separates and recovers the solid residue not distilled；
B reacts isolated mixed organic acid group lease making catalytic decarboxylation is difficult in the distillation component for entering reaction member, obtains hydrocarbon
Class product；
C separates and recovers the hydrocarbon product in separative unit.
11. according to the method described in claim 10, it is characterized in that, the heat that will be generated in fuel element using heating medium
Supply heating unit and reaction member；Heating medium supplies separative unit after reaction member absorbs heat；
Preferably, it when containing more than two sublimation units in heating unit, will be generated in fuel element using heating medium
Heat for giving in an adjacent sublimation unit of reaction member, heating medium after the sublimation unit absorbs heat along and object
Stream moves opposite method and successively supplies a upper sublimation unit adjacent thereto.
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