CN110724034B - Method for relieving residual liquid blockage of molybdenum-containing catalyst in tertiary butanol refining process - Google Patents
Method for relieving residual liquid blockage of molybdenum-containing catalyst in tertiary butanol refining process Download PDFInfo
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- CN110724034B CN110724034B CN201910902059.2A CN201910902059A CN110724034B CN 110724034 B CN110724034 B CN 110724034B CN 201910902059 A CN201910902059 A CN 201910902059A CN 110724034 B CN110724034 B CN 110724034B
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 108
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 45
- 239000011733 molybdenum Substances 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000007670 refining Methods 0.000 title claims abstract description 32
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 239000002519 antifouling agent Substances 0.000 claims abstract description 29
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- DBKKYJPKNUNYFA-UHFFFAOYSA-N cyclohexylazanium;octadecanoate Chemical compound NC1CCCCC1.CCCCCCCCCCCCCCCCCC(O)=O DBKKYJPKNUNYFA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 5
- 239000012188 paraffin wax Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000116 mitigating effect Effects 0.000 claims 5
- 239000002699 waste material Substances 0.000 abstract description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 13
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 12
- 238000013461 design Methods 0.000 description 9
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006735 epoxidation reaction Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229940094933 n-dodecane Drugs 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005502 peroxidation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/008—Polymeric surface-active agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
- C11D3/181—Hydrocarbons linear
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
- C11D3/2006—Monohydric alcohols
- C11D3/201—Monohydric alcohols linear
- C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- C11D2111/20—
Abstract
The invention discloses a method for slowing down blockage of a molybdenum-containing catalyst residual liquid in a tertiary butanol refining process, wherein a tertiary butanol refining device comprises a first rectifying tower, a first connecting pipeline, a second rectifying tower, a second connecting pipeline and an evaporator which are sequentially communicated, a first conveying pump is arranged on the first connecting pipeline, a second conveying pump is arranged on the second connecting pipeline, and antifouling agents are respectively injected into the first connecting pipeline and the second connecting pipeline and comprise 50-60 parts of direct-connected alkane, 10-20 parts of heavy paraffin, 3-5 parts of long-chain fatty alcohol and 1-3 parts of cyclohexylamine stearate. The method for relieving the blockage of the molybdenum-containing catalyst raffinate in the tertiary butanol refining process effectively relieves the blockage of the molybdenum-containing catalyst raffinate in the tertiary butanol refining process, so that the service cycle of each device and each pipeline in the butanol refining process is prolonged by more than four times; the yield of the molybdenum-containing waste liquid is reduced by more than half, and the treatment cost is obviously reduced; the operation temperature of the tower kettle is improved, and the recovery rate of the tertiary butanol is improved.
Description
Technical Field
The invention relates to a method for slowing down the blockage of a molybdenum-containing catalyst residual liquid in a tertiary butanol refining process, and belongs to the field of propylene oxide coproduction.
Background
The coproduction process of the propylene oxide/methyl tert-butyl ether (PO/MTBE) mainly comprises peroxidation, epoxidation, TBA/PO (tert-butyl alcohol/propylene oxide) refining, MTBE refining and the like. The PO/MTBE coproduction process comprises the steps of carrying out peroxidation on isobutane and oxygen to generate an intermediate product tert-butyl hydroperoxide (TBHP), carrying out epoxidation reaction on the generated intermediate product tert-butyl hydroperoxide (TBHP) and propylene under the action of a molybdenum-containing catalyst to generate Propylene Oxide (PO) and tert-butyl alcohol (TBA), and reacting the refined TBA with methanol to synthesize MTBE, wherein metal molybdenum residual liquid in the epoxidation reaction can enter a TBA refining unit. After the molybdenum raffinate enters the TBA refining unit, the molybdenum raffinate is easy to accumulate in a tower kettle reboiler, a tower kettle pump and a discharge pipeline, and after the molybdenum raffinate is accumulated to a certain degree, the tower kettle pump and a downstream pipeline are blocked, so that the heat exchange efficiency of a heat exchanger is reduced, and the molybdenum raffinate needs to be frequently switched and processed.
At present, in order to relieve the blockage problem of a tower kettle pump, a discharge pipeline and the like, the recovery rate of effective components can be reduced only by reducing the operation temperature of the tower kettle and improving the discharge flow of the tower kettle, so that the service cycle of a tower kettle reboiler, the tower kettle pump and the discharge pipeline is prolonged. And finally discharging the molybdenum-containing waste liquid entering the TBA refining unit from the epoxidation unit to a catalyst waste liquid tank through a recovery device, and conveying the molybdenum-containing waste liquid to a hazardous waste operation unit for hazardous waste incineration. The designed production amount of the molybdenum-containing waste liquid is about 1.88t/h, calculated according to 8000 hours of annual operation, and 5000 yuan of treatment cost per ton, and the treatment cost of the molybdenum-containing waste liquid is 7500 ten thousand yuan per year, namely, the treatment cost of the molybdenum-containing waste liquid is a huge expense at present. Therefore, there is a need to find a more effective method for preventing the blockage, reducing the amount of the molybdenum-containing waste liquid, and reducing the cost for treating the molybdenum-containing waste liquid.
Disclosure of Invention
In order to solve the problems that during the coproduction of propylene oxide/methyl tert-butyl ether (PO/MTBE), molybdenum raffinate is easy to be dumped after entering a TBA refining unit and the like in the prior art, the invention provides a method for relieving the blockage of the molybdenum-containing catalyst raffinate in the refining process of tert-butyl alcohol.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for relieving blockage of a molybdenum-containing catalyst residual liquid in a tertiary butanol refining process is characterized in that a tertiary butanol refining device comprises a first rectifying tower, a first connecting pipeline, a second rectifying tower, a second connecting pipeline and an evaporator which are sequentially communicated, a first conveying pump is arranged on the first connecting pipeline, a second conveying pump is arranged on the second connecting pipeline, and antifouling agents are respectively injected into the first connecting pipeline and the second connecting pipeline and comprise 50-60 parts of direct-connected alkane, 10-20 parts of heavy paraffin, 3-5 parts of long-chain fatty alcohol and 1-3 parts of cyclohexylamine stearate, wherein the parts are parts by mass.
The top discharge of the first rectifying tower and the second rectifying tower is tert-butyl alcohol with purity of more than 95 percent, and the tert-butyl alcohol is sent to react with methanol to generate MTBE.
Before the antifouling agent is not adopted, the treatment capacity of the first rectifying tower is about 100t/h, the concentration of molybdenum-containing waste liquid in the tower kettle discharge is lower, and the service cycle of a tower kettle reboiler and a discharge pipeline is longer; the feeding flow in the second rectifying tower is small, about 6.5-6.6 t/h (most of materials are rectified and separated in the first rectifying tower), the molybdenum-containing waste liquid is concentrated in a tower kettle reboiler and a discharge pipe line, and the operation periods of the tower kettle discharge pipe line, the tower kettle reboiler and the tower kettle discharge pump are short; this application adds the antifouling agent of specific constitution on first connecting line and second connecting line, has effectively alleviated the jam problem of second rectifying column and follow-up pipeline, has reduced the output of molybdenum-containing waste liquid simultaneously, is showing and is reducing treatment cost, has improved tert-butyl alcohol's rate of recovery.
In order to further improve the anti-blocking effect, the anti-fouling agent further comprises 5-8 parts of diammine and 0.5-2 parts of nonylphenol polyoxyethylene ether, wherein the parts are in parts by weight.
In order to further improve the anti-clogging effect, the number of carbon atoms of the straight-chain alkane is preferably from C9 to C12; the carbon number of the long-chain fatty alcohol is C8-C12.
The antifouling agent has the effect of prolonging the service cycle of residual liquid equipment of the molybdenum-containing catalyst; the inventor finds out through research that: for equipment or pipelines containing the molybdenum catalyst raffinate, the antifouling agent plays a role through the oleophilic group and the polar group contained in the antifouling agent, and insoluble solid or liquid substances in materials can be wrapped to form micelles, so that the solubility of the materials to the insoluble solid or liquid substances is improved; meanwhile, the new generated carbon deposition and other solid small particles in the system can be adsorbed to form micelles which are dissolved in the material, and the substances are prevented from being condensed into large particles to be deposited on the surface of equipment; for the dirt which is deposited on the surface of the equipment, the dirt can be stripped and washed by adsorbing the polar group of the dispersing agent on the surface of the dirt.
In order to further improve the anti-blocking effect, the mass ratio of the injection amount of the anti-fouling agent on the first connecting pipeline to the material in the first rectifying tower is 175-200 ppm; the mass ratio of the injection amount of the antifouling agent on the second connecting pipeline to the materials in the second rectifying tower is 230-250 ppm.
In order to increase the purity of the tert-butanol obtained, a first rectification column: the pressure in the tower is 26 +/-2 kpa absolute, the temperature at the bottom of the tower is 80 +/-3 ℃, and the temperature at the top of the tower is 48 +/-3 ℃; a second rectifying tower: the pressure in the tower is 24 +/-2 kpa absolute, the temperature at the bottom of the tower is 83 +/-3 ℃, and the temperature at the top of the tower is 50 +/-3 ℃.
In order to improve the recovery rate of the tertiary butanol and ensure the anti-blocking effect, the temperature in the first connecting pipeline is 80 +/-3 ℃, and the pressure is 0.4 +/-0.1 MPa gauge pressure; the temperature in the second connecting pipeline is 83 +/-3 ℃, and the pressure is 0.8 +/-0.1 MPa gauge pressure.
In order to facilitate feeding, the tert-butyl alcohol refining device further comprises an antifouling agent tank, the antifouling agent tank is communicated with the first connecting pipeline through a third connecting pipeline, the antifouling agent tank is communicated with the second connecting pipeline through a fourth connecting pipeline, the third connecting pipeline is provided with a first metering pump, and the fourth connecting pipeline is provided with a second metering pump; and a first check valve is arranged on a third connecting pipeline at the downstream of the first metering pump, and a second check valve is arranged on a fourth connecting pipeline at the downstream of the second metering pump.
In order to facilitate the treatment, the device also comprises a light component recovery tank and a catalyst residue tank; one end of the first connecting pipeline is communicated with the bottom of the side wall of the first rectifying tower, and the other end of the first connecting pipeline is communicated with the middle part of the side wall of the second rectifying tower; one end of the second connecting pipeline is communicated with the bottom of the side wall of the second rectifying tower, and the other end of the second connecting pipeline is communicated with the middle part of the evaporator; the bottom of the evaporator is communicated with the catalyst residue tank through a fifth pipeline, and the top of the evaporator is communicated with the light component recovery tank through a sixth pipeline. Namely after the material enters a first rectifying tower for rectification, the material discharged from the top of the tower is tertiary butanol with the purity of more than 95 percent, the material discharged from the bottom of the tower is sent to a second rectifying tower, the material discharged from the top of the second rectifying tower is tertiary butanol with the purity of more than 95 percent, the material discharged from the bottom of the tower is sent to an evaporator, and light components in the material are evaporated from the top by the evaporator and sent to a light component recovery tank to be used as fuel; and the material at the bottom of the evaporator is sent to a catalyst residue tank. Under the current operating mode, the catalyst residue jar material is sent to the useless producer of factory external danger and is burned, and the heat of burning can produce partial steam for the heat supply.
Conventional equipment such as a delivery pump, a meter and the like can be arranged on each pipeline according to requirements.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The method for relieving the blockage of the molybdenum-containing catalyst raffinate in the tertiary butanol refining process effectively relieves the blockage of the molybdenum-containing catalyst raffinate in the tertiary butanol refining process, so that the service cycle of each device and each pipeline in the butanol refining process is prolonged by more than four times; the yield of the molybdenum-containing waste liquid is reduced by more than half, and the treatment cost is obviously reduced; the operation temperature of the tower kettle is improved, and the recovery rate of the tertiary butanol is improved.
Drawings
FIG. 1 is a flow diagram of a process for the co-production of propylene oxide/methyl tert-butyl ether (PO/MTBE);
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
The tertiary butanol refining device comprises a first rectifying tower, a first connecting pipeline, a second rectifying tower, a second connecting pipeline, a feeding heat exchanger, an evaporator, a catalyst residue tank and an antifouling agent tank which are sequentially communicated, wherein the antifouling agent tank is communicated with the first connecting pipeline through a third connecting pipeline; a third connecting pipeline at the downstream of the first metering pump is provided with a first check valve, and a fourth connecting pipeline at the downstream of the second metering pump is provided with a second check valve; one end of the first connecting pipeline is communicated with the bottom of the side wall of the first rectifying tower, and the other end of the first connecting pipeline is communicated with the middle part of the side wall of the second rectifying tower; one end of the second connecting pipeline is communicated with the bottom of the side wall of the second rectifying tower, and the other end of the second connecting pipeline is communicated with the middle part of the evaporator; the bottom of the evaporator is communicated with the catalyst residue tank through a fifth pipeline, and the top of the evaporator is communicated with the light component recovery tank through a sixth pipeline. After the crude TBA material enters a first rectifying tower for rectification, the top and survey line discharge is tert-butyl alcohol with the purity of more than 95 percent, the bottom material is sent to a second rectifying tower, the top discharge of the second rectifying tower is tert-butyl alcohol with the purity of more than 95 percent, the bottom material is sent to an evaporator, light components in the material are evaporated from the top by the evaporator and sent to a light component recovery tank to be used as fuel; the material at the bottom of the evaporator is sent to a catalyst residue tank, the molybdenum element in the crude TBA material, except for the part deposited on each element, flows into the catalyst residue tank, and the amount brought out from the top of the rectifying tower and the top of the evaporator is very little and can be ignored. Under the current operating mode, the catalyst residue jar material is sent to the useless producer of factory external danger and is burned, and the heat of burning can produce partial steam for the heat supply.
The antifouling agent comprises 30 parts of n-dodecane, 10 parts of n-nonane, 15 parts of n-decane, 15 parts of heavy paraffin (300# heavy liquid paraffin), 3 parts of n-octanol, 1 part of n-dodecanol, 2 parts of cyclohexylamine stearate, 6 parts of dipentylamine and 1 part of nonylphenol polyoxyethylene ether (Jiangsu province, Haian petrochemical plant), wherein the parts are in parts by mass.
In each case, the molybdenum catalyst used in the epoxidation reaction was prepared by reacting ammonium dimolybdate with excess ethylene glycol at 97 ℃ under vacuum until no more water was formed, and the molybdenum content in the molybdenum catalyst was 8.6 wt%, and the water content was <0.2 wt%.
The temperature in the first connecting pipeline is 80 ℃, the pressure is 0.4Mpa gauge pressure, and the mass ratio of the injection quantity of the antifouling agent in the first connecting pipeline to the material in the first rectifying tower is 180 ppm; the temperature in the second connecting pipeline is 83 ℃, the pressure is 0.8Mpa gauge pressure, and the mass ratio of the injection amount of the antifouling agent in the second connecting pipeline to the material in the second rectifying tower is 235 ppm.
A first rectifying tower: the pressure in the tower is 26kpa absolute pressure, the temperature at the bottom of the tower is 80 ℃, the temperature at the top of the tower is 48 ℃, the treatment capacity of the first rectifying tower is about 100t/h, and the content of molybdenum element in the crude TBA material entering the first rectifying tower is 0.047%; a second rectifying tower: the pressure in the tower is 24kpa absolute, the temperature at the bottom of the tower is 83 ℃, the temperature at the top of the tower is 50 ℃, and the treatment capacity of the second rectifying tower is about 5.5 t/h; the treatment capacity of the evaporator is about 3.3 t/h; the design value of the yield of the molybdenum-containing waste liquid is 0.9 t/h. The discharge of the top of the first rectifying tower and the discharge of the measuring line are tertiary butanol with the purity of more than 95 percent, the discharge of the top of the second rectifying tower is tertiary butanol with the purity of more than 95 percent, the discharge of the light component at the top of the evaporator is 2.4t/h, and the discharge of the molybdenum-containing waste liquid at the bottom of the evaporator is 0.9 t/h.
Through online statistics, the design service cycle of the reboiler at the tower bottom of the first rectifying tower is 3 years, the normal use is not influenced after the reboiler is used for 3 years, and the design cycle is required to be maintained for ensuring safety even if the normal use is not influenced; the service cycle of the forced circulation pump of the tower kettle reboiler of the second rectifying tower is more than 16 days, the design service cycle of the tower kettle reboiler of the second rectifying tower is 2 years, the normal use is not influenced after the tower kettle reboiler of the second rectifying tower is used for 2 years, and the maintenance is needed to ensure the safety even if the normal use is not influenced by the design cycle; the service cycle of the second connecting pipeline is more than 1 year, the service cycle of the second transfer pump is more than 6 weeks, and the service cycle of the feeding heat exchanger is more than about 200 days. Compared with the recovery amount of the tertiary butanol of the first rectifying tower in the comparative example 1, the recovery amount of the tertiary butanol is improved by 1.1 t/h; the recovery amount of the tertiary butanol of the second rectifying tower is improved by 0.4 t/h.
Comparative example 1
The tertiary butanol refining device comprises a first rectifying tower, a first connecting pipeline, a second rectifying tower, a second connecting pipeline, a feeding heat exchanger, an evaporator and a catalyst residue tank which are sequentially communicated; one end of the first connecting pipeline is communicated with the bottom of the side wall of the first rectifying tower, and the other end of the first connecting pipeline is communicated with the middle part of the side wall of the second rectifying tower; one end of the second connecting pipeline is communicated with the bottom of the side wall of the second rectifying tower, and the other end of the second connecting pipeline is communicated with the middle part of the evaporator; the bottom of the evaporator is communicated with the catalyst residue tank through a fifth pipeline, and the top of the evaporator is communicated with the light component recovery tank through a sixth pipeline; and a first conveying pump is arranged on the first connecting pipeline, and a second conveying pump is arranged on the second connecting pipeline.
A first rectifying tower: the pressure in the tower is 26kpa absolute pressure, the temperature at the bottom of the tower is 78 ℃, the temperature at the top of the tower is 48 ℃, the treatment capacity of the first rectifying tower is about 100t/h, and the content of molybdenum element in the crude TBA material entering the first rectifying tower is 0.047%; a second rectifying tower: the pressure in the tower is 24kpa absolute, the temperature at the bottom of the tower is 80 ℃, the temperature at the top of the tower is 50 ℃, and the treatment capacity of the second rectifying tower is about 6.6 t/h; the treatment capacity of the evaporator is about 4.8 t/h; the yield of the molybdenum-containing waste liquid is 1.88 t/h. The temperature in the first connecting pipeline is 78 ℃, and the pressure is 0.4Mpa gauge pressure; the temperature in the second connecting pipeline is 80 ℃, and the pressure is 0.8Mpa gauge pressure. The top discharge of the first rectifying tower and the second rectifying tower is tertiary butanol with the purity of more than 95 percent. The composition of the feed to the first rectification column was exactly the same as in example 1 and was the same sample. The discharge of the top of the first rectifying tower and the discharge of the measuring line are respectively 93.4t/h of tertiary butanol with the purity of more than 95 percent, the discharge of the top of the second rectifying tower is 1.8t/h of tertiary butanol with the purity of more than 95 percent, the discharge of light components at the top of the evaporator is 2.92t/h, and the discharge of molybdenum-containing waste liquid at the bottom of the evaporator is 1.88 t/h.
Through online statistics, the service cycle of the forced circulation pump of the tower kettle reboiler of the second rectifying tower is 3 days, the design service cycle of the tower kettle reboiler of the second rectifying tower is 6 months, when the forced circulation pump is used for 6 months, normal use is affected, maintenance and removal are carried out, the service cycle of the second connecting pipeline is about 90 days, the service cycle of the second conveying pump is 1 week, and the service cycle of the feeding heat exchanger is about 70 days. The blockage can be more severe if the discharge at the bottom of the rectifying tower and the discharge at the bottom of the evaporator are reduced.
As is evident from comparing example 1 with comparative example 1: in the embodiment 1, the specific amount and the specific composition of the antifouling agent are added at the specific position, so that the tower bottom temperature of the rectifying tower is improved, the recovery rate of the tert-butyl alcohol is improved, the discharging of a tower kettle of the rectifying tower is reduced, the yield of the molybdenum-containing waste liquid is reduced by more than half, the service cycle of each device and each pipeline is obviously prolonged, and the effect is very obvious.
Example 2
Essentially the same as in example 1, except that: the antifouling agent comprises 35 parts of n-dodecane, 15 parts of n-decane, 20 parts of heavy paraffin (300# heavy liquid paraffin), 2 parts of n-octanol, 1 part of n-dodecanol, 3 parts of cyclohexylamine stearate, 5 parts of dipentylamine and 1.5 parts of nonylphenol polyoxyethylene ether, wherein the parts are in parts by mass.
The mass ratio of the injection amount of the antifouling agent on the first connecting pipeline to the material in the first rectifying tower is 190 ppm; the mass ratio of the injection amount of the antifouling agent on the second connecting pipeline to the material in the second rectifying tower is 245 ppm.
Through online statistics, the design service cycle of the reboiler at the tower bottom of the first rectifying tower is 3 years, the normal use is not influenced after the reboiler is used for 3 years, and the design cycle is required to be maintained for ensuring safety even if the normal use is not influenced; the forced circulation pump service cycle of the second rectifying tower kettle reboiler is more than 15 days, the design service cycle of the second rectifying tower kettle reboiler is 2 years, the second rectifying tower kettle reboiler is used for 2 years, the normal use is not influenced, the second rectifying tower kettle reboiler is still overhauled and cleared, the service cycle of the second connecting pipeline is more than 1 year, the service cycle of the second conveying pump is more than 6 weeks, and the service cycle of the feeding heat exchanger is more than about 200 days. The improvement in recovery of tertiary butanol compared to comparative example 1 is similar to example 1.
Claims (6)
1. A method for slowing down the blockage of the residual liquid of a molybdenum-containing catalyst in the refining process of tertiary butanol is characterized by comprising the following steps:
the tertiary butanol refining device comprises a first rectifying tower, a first connecting pipeline, a second rectifying tower, a second connecting pipeline and an evaporator which are sequentially communicated, wherein one end of the first connecting pipeline is communicated with the bottom of the side wall of the first rectifying tower, and the other end of the first connecting pipeline is communicated with the middle of the side wall of the second rectifying tower; one end of the second connecting pipeline is communicated with the bottom of the side wall of the second rectifying tower, and the other end of the second connecting pipeline is communicated with the middle part of the evaporator; a first conveying pump is arranged on the first connecting pipeline, a second conveying pump is arranged on the second connecting pipeline, and antifouling agents are respectively injected into the first connecting pipeline and the second connecting pipeline;
the antifouling agent comprises 50-60 parts of straight-chain alkane, 10-20 parts of heavy paraffin, 3-5 parts of long-chain fatty alcohol, 1-3 parts of cyclohexylamine stearate, 5-8 parts of diamylamine and 0.5-2 parts of nonylphenol polyoxyethylene ether, wherein the parts are in parts by weight;
the crude TBA material enters a first rectifying tower for rectification, and the material at the bottom of the first rectifying tower enters a second rectifying tower; a first rectifying tower: the pressure in the tower is 26 +/-2 kpa absolute, the temperature at the bottom of the tower is 80 +/-3 ℃, and the temperature at the top of the tower is 48 +/-3 ℃; a second rectifying tower: the pressure in the tower is 24 +/-2 kpa absolute, the temperature at the bottom of the tower is 83 +/-3 ℃, and the temperature at the top of the tower is 50 +/-3 ℃.
2. The method for mitigating plugging of the molybdenum-containing catalyst raffinate from the refining of tert-butanol according to claim 1, wherein: the number of carbon atoms of the straight-chain alkane is C9-C12; the carbon number of the long-chain fatty alcohol is C8-C12.
3. The method for mitigating plugging of the molybdenum-containing catalyst raffinate from the refining of t-butanol according to claim 1 or 2, wherein: the mass ratio of the injection amount of the antifouling agent on the first connecting pipeline to the material in the first rectifying tower is 175-200 ppm; the mass ratio of the injection amount of the antifouling agent on the second connecting pipeline to the materials in the second rectifying tower is 230-250 ppm.
4. The method for mitigating plugging of the molybdenum-containing catalyst raffinate from the refining of t-butanol according to claim 1 or 2, wherein: the temperature in the first connecting pipeline is 80 +/-3 ℃, and the pressure is 0.4 +/-0.1 MPa of gauge pressure; the temperature in the second connecting pipeline is 83 +/-3 ℃, and the pressure is 0.8 +/-0.1 MPa gauge pressure.
5. The method for mitigating plugging of the molybdenum-containing catalyst raffinate from the refining of t-butanol according to claim 1 or 2, wherein: the tertiary butanol refining device further comprises an antifouling agent tank, the antifouling agent tank is communicated with the first connecting pipeline through a third connecting pipeline, the antifouling agent tank is communicated with the second connecting pipeline through a fourth connecting pipeline, the third connecting pipeline is provided with a first metering pump, and the fourth connecting pipeline is provided with a second metering pump; and a first check valve is arranged on a third connecting pipeline at the downstream of the first metering pump, and a second check valve is arranged on a fourth connecting pipeline at the downstream of the second metering pump.
6. The method for mitigating plugging of the molybdenum-containing catalyst raffinate from the refining of t-butanol according to claim 1 or 2, wherein: the tertiary butanol refining device also comprises a light component recovery tank and a catalyst residue tank; the bottom of the evaporator is communicated with the catalyst residue tank through a fifth pipeline, and the top of the evaporator is communicated with the light component recovery tank through a sixth pipeline.
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