CN104591962A - Process and device for purifying feed methanol in gasoline production process through methanol conversion - Google Patents
Process and device for purifying feed methanol in gasoline production process through methanol conversion Download PDFInfo
- Publication number
- CN104591962A CN104591962A CN201510016206.8A CN201510016206A CN104591962A CN 104591962 A CN104591962 A CN 104591962A CN 201510016206 A CN201510016206 A CN 201510016206A CN 104591962 A CN104591962 A CN 104591962A
- Authority
- CN
- China
- Prior art keywords
- methyl alcohol
- scavenging tower
- methanol
- tower
- acidic resins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/14—Controlling or regulating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a process for purifying feed methanol in a gasoline production process through methanol conversion, wherein acidic resin is filled in a 1# purifying tower and a 2# purifying tower and pre-processed by using a saline solution and a diluted hydrochloric acid solution; when the content of basic nitride in the feed methanol is less than 700 ppm, the feed methanol is simultaneously fed into the 1# purifying tower and the 2# purifying tower to be purified; when the content of the basic nitride in the feed methanol is more than or equal to 700 ppm, a purifying system is rapidly switched so that the two towers are connected in series by opening and closing a valve; and thus, all the feed methanol only can be fed into a synthetic oil system after being purified by the two purifying towers connected in series. The process disclosed by the invention has the advantages of being simple in process and good in purification effect.
Description
Technical field
The invention belongs to a kind of purification process and device of methanol conversion gasoline process Raw methyl alcohol.
Technical background
China has the energy structure of rich coal, oil-poor and weak breath, and especially the imbalance between supply and demand of oil is day by day serious.Coal liquifaction technology meets the adjustment direction of China's energy structure, is to alleviate the most effective approach of petroleum-based energy shortage problem.Coal liquifaction technology is divided into direct liquefaction and indirect liquefaction, wherein indirect liquefaction comprises Fischer-Tropsch (F-T) synthesis and preparing gasoline by methanol (MTG) two kinds of technology, compare with ICL for Indirect Coal Liquefaction F-T synthetic technology with DCL/Direct coal liquefaction, preparing gasoline by methanol have that technique is simple, the reliable and yield of gasoline advantages of higher of technology maturation.Consider developing rapidly of Chemical Industry in recent years simultaneously, make ammonia from coal problem of excess production capacity day by day serious.Therefore, the successful exploitation of technique for preparing gasoline by methanol and industrial applications not only alleviate the problem such as domestic petroleum shortage and methyl alcohol surplus, and have enriched the technological line of coal, have important practical significance.
At present, the fixed bed one step method MTG technique that the fixed bed two-step approach MTG technique of industrial main employing american exxon-Mobil Corp. exploitation and SaiDing Engineering Co., Ltd and coalification are developed cooperatively.The former be first by methyl alcohol at Cu/Al
2o
3on catalyzer, dehydration forms dme, then dme is converted into high-octane gasoline products under the katalysis of ZSM-5; And the latter is methyl alcohol is converted into gasoline products on modified zsm-5 zeolite.Acid sites in ZSM-5 catalyzer is the chief active position of methanol conversion, and space constraint effect can be played in intersection two ducts of catalyzer uniqueness, controls gasoline products at below C11.But molecular sieve pore passage structure is narrower and long, easily cause reactant and product long-time delay and the generation that causes carbon distribution to react in duct, further blocking diffusion admittance and covering active centre make catalyst deactivation, the carbon distribution inactivation of catalyzer belongs to renewable inactivation, can be recovered the activity of catalyzer by air or oxygen combustion.
At present, industry MTG device generally runs 15 ~ 20 days rear catalysts will carbon distribution inactivation, MTG catalyst regeneration 14 ~ 17 all after dates under normal circumstances, catalyzer owing to there occurs efflorescence, duct caves in and the irreversible inactivation such as acid loss and changing, its total treatment capacity reaches 8000 ~ 10000 tons of methyl alcohol/ton catalyzer.But numerous MTG manufacturer finds; often can run into live catalyst filling in process of production in the near future can fast deactivation; separate run times is only 6 ~ 7 days just needs regeneration afterwards; the total treatment capacity of catalyzer is only after 3000 ~ 5000 tons of methyl alcohol/ton catalyzer must more catalyst changeout; not only increase investment and the running cost of catalyzer; and had a strong impact on normally carrying out of production, become numerous MTG producers urgent need to solve the problem.
SaiDing Engineering Co., Ltd and Inner Mongol Qing Hua group rely on the MTG project of the latter 100,000 tons/year, by more catalyst changeout, adjustment working condition, optimize regeneration condition and change the series of measures such as methyl alcohol starting material and the problems referred to above are analyzed and investigates, find catalyzer, working condition and regeneration condition are less to the stability influence produced, and have affect more significantly by changing the stability of methanol feedstock on catalyzer, catalyst characterization after inactivation is found simultaneously, catalyzer after inactivation does not find the phenomenon of caving in of efflorescence and pore passage structure, but it is very fast to find that the acid amount of catalyzer runs off.The above analysis is known, causes the major cause of rapid catalyst deactivation to be that this impurity can cause the loss in acidity of catalyst active centre, and then causes the non-renewable inactivation of catalyzer containing certain impurity in methanol feedstock.Therefore, develop a kind of purification process of MTG charging methyl alcohol, be solve the improper inactivation of MTG catalyzer, ensure the most effective approach of the steady running of producing.
Summary of the invention
The object of the invention is the improper deactivation phenomenom for catalyzer in MTG production process, and it is simple to develop a kind of flow process, the purification process of the methanol conversion gasoline process Raw methyl alcohol of good purification and device.
The present invention effectively eliminates the impurity in methanol feedstock, not only solves the improper deactivation prob of catalyzer, and extends the one way working time of catalyzer further, adds the entire life of number of run and catalyzer.
For reaching above-mentioned purpose, first contriver analyzes the methyl alcohol from different manufacturer, find that in the methyl alcohol that different manufacturers is produced, dopant species reaches kind more than 20, and its content is with methyl alcohol source and batch different generation fluctuation on a large scale, then according to the detection level of impurity in methanol feedstock, by the simultaneous test of the methanol feedstock and pure methanol feedstock of allocating single impurity into is found, the ammonia contained in methyl alcohol, methylamine, the introducing of the basic nitrogen compound such as dimethylamine and Trimethylamine 99 impurity can cause rapidly the inactivation of catalyzer, and the major cause of its inactivation is the loss in acid active centre in catalyzer, this is due to the aobvious alkalescence of alkali nitride compounds, the acid sites generation chemisorption of itself and catalyzer, because this chemisorption intensity is higher, and be difficult to desorption by conventional method, and then cause rapid catalyst deactivation.
Basic nitrogen compound class impurity according to containing in the methyl alcohol obtained above is the major cause causing the improper inactivation of MTG catalyzer, we analyze the content of the basic nitrogen compound in methanol feedstock emphatically, find that the content difference of different methanol feedstock neutral and alkali nitride is huge, its content range is 100 ~ 1000ppm, wherein when basic nitrogen compound content is 1000ppm, fast deactivation after catalyzer single in industrial methanol production equipment runs 7 days, continues through above-mentioned methanol feedstock 30 days thorough inactivations of rear catalyst.We have studied basic nitrogen compound content further by a large amount of lab scales and sideline test affects catalyst stability, find when methyl alcohol neutral and alkali amount of nitrides is lower than 40ppm, catalyst stability is good, and when its content is higher than 40ppm, catalyst deactivation is very fast, normally runs working time and entire life lower than catalyzer.But consider that the impact of basic nitrogen compound on catalyzer is non-renewable, determine basic nitrogen compound content to control at below 20ppm according to knowhow for many years.
The technology removing basic nitrogen compound mainly contains salt pickling, liquid-solid absorption method and complexometry three class, contriver considers the many factors such as technical stability, cost of investment, running cost and removal effect, and select acidic ion exchange resin removing sulfuldioxide according to through engineering approaches experience for many years, further by a large amount of sideline test, have selected kind and the operational condition of resin.When carrying out purification process design, considering that the basic nitrogen compound content scope in methanol feedstock is very big, needing the purification of multistage resin when basic nitrogen compound content is high; And consider the continuity problem of production, produce when ensureing to change resin and normally carry out.Consider above-mentioned factor, contriver is according to sideline test, and the knowhow of the MTG engineering design combined for many years and MTG, develop a kind of double tower purification process, this technique under normal circumstances methanol feedstock parallel connection passes through scavenging tower, but by the load of adjustment two tower, one of them tower is made to bear major part purification load, and another tower is born small portion purification load or is in stand-by state, the charging of this tower is then stopped when first tower decontamination effect improving is not up to standard, and change resin, another tower then carries out the purification of whole charging methyl alcohol, ensure the continuity of producing, when methanol feedstock neutral and alkali amount of nitrides is higher, be difficult to reach purification requirement by single tower, then by the opening and closing of adjustment valve, realize the series connection purification of double tower.Above-mentioned technique and working method not only can effectively purify methyl alcohol, extend working time and the entire life of MTG, and the continuity of production can be realized, and the switching of the series and parallel connections dress bar of double tower can be realized, avoid the higher infringement that catalyzer is caused of content in charging methyl alcohol, there is important theory and realistic meaning.
The purification process of methanol conversion gasoline process Raw methyl alcohol disclosed by the invention comprises the steps:
(1) acidic resins are loaded in 1# scavenging tower and 2# scavenging tower, first salt solution is conveyed in 1# and 2# scavenging tower from top, after soaking acidic resins, salt solution is put only, and by de-salted water to the acidic resins rinsed clean in scavenging tower, then dilute hydrochloric acid solution is conveyed in 1# and 2# scavenging tower from top, after soaking acidic resins, hydrochloric acid soln is put only, and by de-salted water by the acidic resins rinsed clean in scavenging tower, finally nitrogen is sent in two scavenging tower from bottom, and the outlet nitrogen of discharging from top of tower is sent to torch, purge totally until the free-water in acidic resins, complete the pre-treatment of acidic resins,
(2) when the basic nitrogen compound content in methanol feedstock is lower than 700ppm, material benzenemethanol is sent in 1# and 2# scavenging tower from top parallel connection and purifies, by adjusting the flow of two scavenging tower charging methyl alcohol, 70 ~ 90wt% of charging methanol quality mark is made to enter 1# scavenging tower, and remaining 10 ~ 30wt% enters 2# scavenging tower, the methyl alcohol after purification is sent to synthetic oil system after merging;
(3) along with the carrying out of methanol purification, when 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve of 1# scavenging tower, and the acidic resins changed in 1# scavenging tower, and charging methyl alcohol all enters 2# scavenging tower purifies, purifying methanol is sent to synthetic oil system;
(4) after the acidic resins of 1# scavenging tower load, according to step (1), pre-treatment is carried out to the resin in 1# scavenging tower, by the opening and closing of adjustment valve after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 2# scavenging tower, and remaining 50wt% enters 1# scavenging tower, when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve of 2# scavenging tower, and the acidic resins changed in 2# scavenging tower, and charging methyl alcohol all enters 1# scavenging tower purifies, purifying methanol is sent to synthetic oil system,
(5) after the acidic resins of 2# scavenging tower load, according to step (1), pre-treatment is carried out to the resin in 2# scavenging tower, by the opening and closing of adjustment valve after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 1# scavenging tower, and remaining 50wt% enters 2# scavenging tower, the methyl alcohol after purification is sent to synthetic oil system after merging;
(6) repeating step (3) ~ (5) can realize when the continuous purification of methyl alcohol neutral and alkali amount of nitrides lower than methyl alcohol during 700ppm operates;
(7) as two scavenging tower be all in cleansing operation time, when the content >=700ppm of the basic nitrogen compound in material benzenemethanol being detected, then by the opening and closing of adjustment valve, rapidly purification system is switched to cascade towers state, ensure whole charging methyl alcohol all by after two scavenging tower series connection purifications, just can be sent to synthetic oil system;
(8) when any one scavenging tower is in acidic resins filling or regenerative process, and when the content >=700ppm of the basic nitrogen compound in material benzenemethanol being detected, then by the opening and closing of adjustment valve, part methyl alcohol is back to after scavenging tower tower top mixes with fresh methanol to carry out secondary-cleaned, ensure the purity of outlet methyl alcohol.
As above is saturated aqueous common salt for the pretreated salt solution of acidic resins, and soak time is 15 ~ 24h.
Mass concentration as above for the pretreated dilute hydrochloric acid solution of acidic resins is 1 ~ 8wt%, and its soak time is 2 ~ 10h.
The feeding temperature of material benzenemethanol described above is 20 ~ 60 DEG C, and optimum is 30 ~ 50 DEG C.
The acidic resins loaded in scavenging tower as above are CT151 type or the C100E type of drift Lai Te (China) company; The D113 type that Chemical Plant of Nankai Univ. produces, D061 type or D152 type.
In scavenging tower as above, the granularity of acidic resins is 0.5 ~ 1.5mm, and its coefficient of uniformity is 1.5 ~ 2.
Methyl alcohol as above is 1 ~ 30h through the mass space velocity that acidic resins exchange
-1, more excellent is 10 ~ 20h
-1.
In two scavenging tower inlet line, all safety valve is set as above, prevents due to resin blocking that the feed pressure that causes is too high, and the material of safety relief is sent to torch burning.
Methyl alcohol neutral and alkali nitride removal rate after purification described above reaches 94 ~ 98%, outlet methyl alcohol neutral and alkali amount of nitrides≤20ppm.
For realizing object of the present invention, contriver devises scavenging tower further, it comprises housing 1, upper strata wire gauzee filter 2, acidic resins 3, back up pad 4, nitrogen sparger 5, nitrogen inlet tube 6, liquid-phase outlet pipe 7, nitrogen sprayer head 8, lower floor's wire gauzee filter 9, liquid phase shower nozzle 10, fluid inlet pipe 11, nitrogen outlet pipe 12, housing 1 is made up of upper cover, middle cylinder and lower cover, nitrogen outlet pipe 12 is arranged at upper cover top, liquid phase shower nozzle 10 is equipped with in upper cover inside, and upper cover has fluid inlet pipe 11, and liquid phase shower nozzle 10 is connected with fluid inlet pipe 11; Back up pad 4, lower floor's wire gauzee filter 9, acidic resins 3 and upper strata wire gauzee filter 2 is followed successively by from down to up in middle cylinder; Conical nitrogen sparger 5 is equipped with in lower cover inside, and there is liquid phase vent pipe 7 lower cover bottom, has nitrogen inlet tube 6 in liquid phase vent pipe 7 inside, and there is nitrogen sprayer head 8 on nitrogen inlet tube 6 top, and nitrogen sprayer head 8 is positioned at conical nitrogen sparger 5.
The aspect ratio of middle cylinder as above is 3 ~ 10.
The loading height of acidic resins 3 as above and the ratio of middle cylinder height are 0.85 ~ 0.92.
Nitrogen sprayer head 8 as above is upper end closed surrounding hollow outs, ensures that the gas entered from gas phase import radially sprays towards surrounding.
Upper strata as above wire gauzee filter 2 is portable, can move up and down with the conversion of resin volume, and by the compacting of resin.
The present invention compared with prior art, has substantive distinguishing features and marked improvement is:
(1) the present invention analyzes running into the improper inactivation of catalyzer in MTG production, and give concrete purification process and working method, not only solve the improper deactivation phenomenom run in preparing gasoline by methanol, and after increasing purification process of the present invention, catalyzer one way extended to 21 ~ 28 days by 15 ~ 20 days working time, the regeneration period of catalyzer is increased to more than 18 times by 11 ~ 16 times, the total treatment capacity of catalyzer adds nearly 20%, substantially increases stability and the economic benefit of MTG production.
(2) the present invention proposes methanol purification technique and be provided with two scavenging tower, the flexible switching of scavenging tower can be realized, and by distributing the ratio of methanol feeding, inactivation while avoiding two scavenging tower, when a scavenging tower changes resin or pre-treatment, another tower can normally work, and ensure that the continuity of production.
(3) the methanol purification technique that proposes of the present invention is by the setting of pipeline and valve, the flexible switching of parallel two towers/series connection and the operation of partial material circulation secondary purification can be realized, ensure that outlet methyl alcohol that is that cause exceeds standard when charging methyl alcohol neutral and alkali amount of nitrides is too high, has important actual application value.
(4) The present invention gives concrete purification tower structure, by descending the two-layer wire gauzee filter that arranges on an acidic resin, resin not only can be avoided at nitrogen drying and purify the efflorescence loss being, and the portable setting of upper strata wire gauzee filter, to compact and evenly when resin pre-treatment is shunk can be ensured, the liquid phase shower nozzle that simultaneously upper strata is arranged can ensure the more uniform and resin contact of charging, increases its purification efficiency.
Accompanying drawing explanation
Fig. 1 is purification process figure of the present invention.
Fig. 2 is the structure iron of scavenging tower of the present invention.
As shown in the figure, P1, P2, P3a, P3b, P4a, P4b, P5a, P5b, P6a, P6b, P7a, P7b, P8, P9, P10a, P10b are pipeline, and V1, V2, V3a, V3b, V4a, V4b, V5a, V5b, V6a, V6b, V7a, V7b, V8a, V8b, V9a, V9b, V10a, V10b, V11, V12a, V12b are valve; 1 is housing, and 2 is upper strata wire gauzee filters, and 3 is acidic ion exchange resins, and 4 is back up pads of resin, 5 is nitrogen spargers, and 6 is nitrogen inlet tubes, and 7 is liquid-phase outlet pipes, and 8 is nitrogen sprayer heads, 9 is lower floor's wire gauzee filters, and 10 is liquid phase shower nozzles, and 11 is fluid inlet pipes, 12 nitrogen outlet pipes.
Methanol purification technique of the present invention by reference to the accompanying drawings 1, undertaken by following working method further:
(1) acidic resins are loaded in 1# scavenging tower 1 and 2# scavenging tower 2, by valve V2, V3a, V3b valve open, remaining pipes valve closes, first by salt solution through pipeline P2, P3a and P3b is conveyed in 1# and 2# scavenging tower, after soaking resin certain hour, open valve V10a and V10b salt solution to be put only, and by de-salted water to the resin rinsed clean in scavenging tower, valve-off V10a and V10b, then by dilute hydrochloric acid solution through pipeline P2, P3a and P3b sends in 1# and 2# scavenging tower, after soaking resin certain hour, open valve V10a and V10b hydrochloric acid soln to be put only, and by de-salted water by the resin rinsed clean in scavenging tower, open valve V6a, V6b, V7a and V7b, all the other valve closess, finally nitrogen is sent in two scavenging tower from bottom, work off one's feeling vent one's spleen and send torch through P5a and P5b, after the free-water in resin being purged and does, complete the pre-treatment of resin.
(2) when the basic nitrogen compound content in methanol feedstock is lower than 700ppm, open valve V1, V4a, V4b, V5a, V5b, V8a, V8b, V9a, V9b and V11, all the other valve closess, by material benzenemethanol through pipeline P1, P4a and P4b sends in 1# and 2# scavenging tower from top parallel connection and purifies, by adjusting the flow of two scavenging tower charging methyl alcohol, 70 ~ 90wt% of charging methanol quality mark is made to enter 1# scavenging tower, and remaining 10% ~ 30wt% enters 2# scavenging tower, after purification, methyl alcohol is discharged bottom two scavenging tower, and through pipeline P6a, P6b and P9 is sent to synthetic oil system.
(3) along with the carrying out of methanol purification, when 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close input and output material valve V4a, V5a, V8a and V9a of 1# scavenging tower, and the acidic resins changed in 1# scavenging tower, and charging methyl alcohol all enters 2# scavenging tower through pipeline P1 and P4b purifies, purifying methanol is sent to synthetic oil system through pipeline P6b and P9.
(4) after the acidic resins of 1# scavenging tower load, according to step (1), pre-treatment is carried out to the acidic resins in 1# scavenging tower, the input and output material valve V4a of 1# scavenging tower is opened after being disposed, V5a, V8a and V9a, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 2# scavenging tower, and remaining 50wt% enters 1# scavenging tower, when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve V4b of 2# scavenging tower, V5b, V8b and V9b, and the acidic resins changed in 2# scavenging tower, and charging methyl alcohol all enters 1# scavenging tower through pipeline P1 and P4a purifies, purifying methanol is sent to synthetic oil system through pipeline P6a and P9.
(5) after the acidic resins of 2# scavenging tower load, according to step (1), pre-treatment is carried out to the resin in 2# scavenging tower, input and output material valve V4b, V5b, V8b and V9b of 1# scavenging tower is opened after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 1# scavenging tower, and remaining 50wt% enters 2# scavenging tower, purifying methanol is sent to synthetic oil system.
(6) repeating step (3) ~ (5) can realize when the continuous purification of methyl alcohol neutral and alkali amount of nitrides lower than methyl alcohol during 700ppm operates.
(7) when two scavenging tower are all in cleansing operation, and when the basic nitrogen compound content >=700ppm in material benzenemethanol being detected, then by the opening and closing of adjustment valve, rapidly purification system is switched to cascade towers state, ensure whole charging methyl alcohol all by after two scavenging tower series connection purifications, just can be sent to synthetic oil system.As charging methyl alcohol is first purified through 1# scavenging tower, by being operating as of 2# tower purification: open valve V1, V4a, V5a, V8a, V12b, V5b, V8b, V9b and V11, all the other valve closess, methanol feeding first purifies through 1# scavenging tower through pipeline P1 and P4a, purifying methanol is sent to 2# scavenging tower through pipeline P6a, P10a and P4b and carries out secondary-cleaned, and purifying methanol is sent to system for methanol synthesis through P6b and P9.
(8) when there being any one scavenging tower to be in acidic resins filling or regenerative process, and when the content >=700ppm of the basic nitrogen compound in material benzenemethanol being detected, then by the opening and closing of adjustment valve, part methyl alcohol is back to after scavenging tower tower top mixes with fresh methanol to carry out secondary-cleaned, ensure the purity of outlet methyl alcohol.As 1# tower be in resin replacement time, open V1, V4b, V5b, V8b, V9b, V11 and V12b, all the other valve closess, the charging methyl alcohol of basic nitrogen compound content >=700ppm enters 2# scavenging tower through pipeline P1 and P4b, purifying methanol is sent to system for methanol synthesis through pipeline P6b and P9, and another part enters 2# scavenging tower after pipeline P6b and P10a is back to 2# scavenging tower tower top and methanol mixed from pipeline P1, carry out secondary-cleaned, by the opening degree of valve V11 and V9a, quantity of reflux can be controlled.
Embodiment
Below by specific embodiment, the specific embodiment of the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to above-described embodiment.
Embodiment 1
Scavenging tower comprises housing 1, upper strata wire gauzee filter 2, acidic resins 3, back up pad 4, nitrogen sparger 5, nitrogen inlet tube 6, liquid-phase outlet pipe 7, nitrogen sprayer head 8, lower floor's wire gauzee filter 9, liquid phase shower nozzle 10, fluid inlet pipe 11, nitrogen outlet pipe 12, housing 1 is made up of upper cover, middle cylinder and lower cover, and upper cover top is provided with nitrogen outlet pipe 12, liquid phase shower nozzle 10 is equipped with in upper cover inside, and upper cover side is provided with fluid inlet 11; Back up pad 4, lower floor's wire gauzee filter 9, acidic resins 3 and upper strata wire gauzee filter 2 is followed successively by from down to up in middle cylinder; Conical nitrogen sparger 5 is equipped with in lower cover inside, and there is liquid phase vent pipe 7 lower cover bottom, has nitrogen inlet tube 6 in liquid phase vent pipe 7 inside, and nitrogen inlet tube 6 top is provided with nitrogen sprayer head 8, and nitrogen sprayer head 8 is positioned at conical nitrogen sparger 5.
The aspect ratio of described middle cylinder is 3.
The loading height of described acidic resins 3 and the ratio of middle cylinder height are 0.85.
Described nitrogen sprayer head 8 is upper end closed surrounding hollow outs, ensures that the gas entered from gas phase import radially sprays towards surrounding.
Described upper strata wire gauzee filter 2 is portable, can move up and down with the conversion of resin volume, and by the compacting of resin.
Be used in the purification process of preparing gasoline by methanol charging methyl alcohol by the scavenging tower that the present embodiment designs, and to adopt containing the methyl alcohol of basic nitrogen compound 600ppm be scavenging tower charging, by reference to the accompanying drawings 1, concrete operation step is as follows:
(1) be 0.5 ~ 1.5mm by granularity, uniformity ratio be 1.5 drift Lai Te (China) company CT151 type acidic resins be loaded in 1# scavenging tower 1 and 2# scavenging tower 2, by valve V2, V3a, V3b valve open, remaining pipes valve closes, first by saturated aqueous common salt through pipeline P2, P3a and P3b is conveyed in 1# and 2# scavenging tower, after soaking resin 15h, open valve V10a and V10b salt solution to be put only, and by de-salted water to the resin rinsed clean in scavenging tower, valve-off V10a and V10b, then be that 1wt% dilute hydrochloric acid solution is through pipeline P2 by mass concentration, P3a and P3b sends in 1# and 2# scavenging tower, after soaking resin 10h, open valve V10a and V10b hydrochloric acid soln to be put only, and by de-salted water by the resin rinsed clean in scavenging tower, open valve V6a, V6b, V7a and V7b, all the other valve closess, finally nitrogen is sent in two scavenging tower from bottom, work off one's feeling vent one's spleen and send torch through P5a and P5b, after the free-water in resin being purged and does, complete the pre-treatment of resin.
(2) valve V1, V4a, V4b, V5a, V5b, V8a, V8b, V9a, V9b and V11 is opened, all the other valve closess, by temperature be 20 DEG C material benzenemethanol through pipeline P1, P4a and P4b from top parallel connection send in 1# and 2# scavenging tower, be 5h at mass space velocity
-1purifying, by adjusting the flow of two scavenging tower charging methyl alcohol, make the 70wt% of charging methanol quality mark enter 1# scavenging tower, and remaining 30wt% entering 2# scavenging tower, after purification, methyl alcohol is sent to synthetic oil system through pipeline P6a, P6b and P9.
(3) along with the carrying out of methanol purification, when 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close input and output material valve V4a, V5a, V8a and V9a of 1# scavenging tower, and the acidic ion exchange resin changed in 1# scavenging tower, and charging methyl alcohol all enters 2# scavenging tower through pipeline P1 and P4b purifies, purifying methanol is sent to synthetic oil system through pipeline P6b and P9.
(4) after the acidic ion exchange resin of 1# scavenging tower loads, according to step (1), pre-treatment is carried out to the resin in 1# scavenging tower, the input and output material valve V4a of 1# scavenging tower is opened after being disposed, V5a, V8a and V9a, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 2# scavenging tower, and remaining 50wt% enters 1# scavenging tower, when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve V4b of 2# scavenging tower, V5b, V8b and V9b, and the acidic ion exchange resin changed in 2# scavenging tower, and charging methyl alcohol all enters 1# scavenging tower through pipeline P1 and P4a purifies, purifying methanol is sent to synthetic oil system through pipeline P6a and P9.
(5) after the acidic ion exchange resin of 2# scavenging tower loads, according to step (1), pre-treatment is carried out to the resin in 2# scavenging tower, input and output material valve V4b, V5b, V8b and V9b of 1# scavenging tower is opened after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 1# scavenging tower, and remaining 50wt% enters 2# scavenging tower, purifying methanol is sent to synthetic oil system.
(6) repeating step (3) ~ (5) can realize when the continuous purification of methyl alcohol neutral and alkali amount of nitrides lower than methyl alcohol during 700ppm operates.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 98%, outlet basic nitrogen compound content is 12 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 24 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 12960 tons of methyl alcohol/ton catalyzer.
Embodiment 2
The aspect ratio of scavenging tower middle cylinder is 5, and the loading height of acidic resins 3 and the ratio of middle cylinder height are 0.87, all the other logical embodiments 1.
The present embodiment adopts the methyl alcohol containing basic nitrogen compound 300ppm as scavenging tower charging, drift Lai Te (China) the company C100E type acidic resins that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.8, saturated common salt water soaking resin 20h, mass concentration is that 4wt% dilute hydrochloric acid solution soaks resin 9h, material benzenemethanol inlet temperature is 40 DEG C, and the mass space velocity of its purification is 13h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 96%, outlet basic nitrogen compound content is 16 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 26 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 14040 tons of methyl alcohol/ton catalyzer.
Embodiment 3
The aspect ratio of scavenging tower middle cylinder is 7, and the loading height of acidic resins 3 and the ratio of middle cylinder height are 0.89, all the other logical embodiments 1.
The present embodiment adopts the methyl alcohol containing basic nitrogen compound 200ppm as scavenging tower charging, the D113 type resin that Chemical Plant of Nankai Univ. that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.9 produces, saturated common salt water soaking resin 22h, mass concentration is that 7wt% dilute hydrochloric acid solution soaks resin 5h, material benzenemethanol inlet temperature is 50 DEG C, and the mass space velocity of its purification is 25h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 95%, outlet basic nitrogen compound content is 10 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 23 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 12420 tons of methyl alcohol/ton catalyzer.
Embodiment 4
The aspect ratio of scavenging tower middle cylinder is 9, and the loading height of acidic resins 3 and the ratio of middle cylinder height are 0.90, all the other logical embodiments 1.
The present embodiment adopts the methyl alcohol containing basic nitrogen compound 100ppm as scavenging tower charging, the D061 type resin that Chemical Plant of Nankai Univ. that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 2.0 produces, saturated common salt water soaking resin 24h, mass concentration is that 7wt% dilute hydrochloric acid solution soaks resin 2h, material benzenemethanol inlet temperature is 60 DEG C, and the mass space velocity of its purification is 30h
-1, all the other are with embodiment 1.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 94%, outlet basic nitrogen compound content is 6 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 28 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 14460 tons of methyl alcohol/ton catalyzer.
Embodiment 5
The aspect ratio of scavenging tower middle cylinder is 10, and the loading height of acidic resins 3 and the ratio of middle cylinder height are 0.92, all the other logical embodiments 1.
The present embodiment is 600ppm at normal charging methanol concentration, when cleansing operation is in step (2) of embodiment 1, namely when two scavenging tower are in parallel operation, catch sight of methyl alcohol neutral and alkali amount of nitrides up to 1000ppm, its whole charging methyl alcohol is first purified by 1# scavenging tower, then through the purification of 2# scavenging tower, when its operation steps and working method are:
(1) valve V1, V4a, V5a, V8a, V12b, V5b, V8b, V9b and V11 is opened, all the other valve closess, methanol feeding first purifies through 1# scavenging tower through pipeline P1 and P4a, purifying methanol is sent to 2# scavenging tower through pipeline P6a, P10a and P4b and carries out secondary-cleaned, and purifying methanol is sent to synthesis system through P6b and P9.
(2) when detecting that methyl alcohol neutral and alkali amount of nitrides reduces to below 700ppm, then by the opening and closing of valve, purification system is adjusted to the state of step (2) in embodiment 1, and repeating step (3) ~ (5) purify.
The concrete operational condition of the present embodiment is:
The D152 type resin that Chemical Plant of Nankai Univ. that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.6 produces, saturated common salt water soaking resin 18h, mass concentration is that 2wt% dilute hydrochloric acid solution soaks resin 9h, and material benzenemethanol inlet temperature is 30 DEG C, and the mass space velocity of its purification is 1h
-1, when parallel two towers, the charging of one of them tower accounts for the 90wt% of charging methanol quality mark, and residue 10wt% enters another scavenging tower.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 98%, outlet basic nitrogen compound content is 12 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the JX6201 type MTG catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 22 days, the regeneration period 18 times, the total treatment capacity of unit catalyst 11880 tons of methyl alcohol/ton catalyzer.
Embodiment 6
The aspect ratio of scavenging tower middle cylinder is 10, and the loading height of acidic resins 3 and the ratio of middle cylinder height are 0.92, all the other logical embodiments 1.
The present embodiment is 600ppm at normal charging methanol concentration, when cleansing operation is in step (2) of embodiment 1, namely when 1# scavenging tower is in and changes resin and pretreatment stage, catch sight of methyl alcohol neutral and alkali amount of nitrides up to 1000ppm, its whole charging methyl alcohol all enters the purification of 2# scavenging tower, and carry out reflux operation, when its operation steps and working method are:
(1) V1, V4b, V5b, V8b, V9b, V11 and V12b is opened, all the other valve closess, the charging methyl alcohol of basic nitrogen compound content >=700ppm enters 2# scavenging tower through pipeline P1 and P4b, purifying methanol is sent to system for methanol synthesis through pipeline P6b and P9, and another part enters 2# scavenging tower after pipeline P6b and P10a is back to 2# scavenging tower tower top and methanol mixed from pipeline P1, carry out secondary-cleaned, by the opening degree of valve V11 and V9a, can quantity of reflux be controlled.
(2) when detecting that methyl alcohol neutral and alkali amount of nitrides reduces to below 700ppm, then by the opening and closing of valve, purification system is adjusted to the state of step (3) in embodiment 1, and repeating step (3) ~ (5) purify.
The concrete operational condition of the present embodiment is:
Drift Lai Te (China) the company C100E type acidic resins that employing granularity is 0.5 ~ 1.5mm, uniformity ratio is 1.6, saturated common salt water soaking resin 18h, mass concentration is that 2wt% dilute hydrochloric acid solution soaks resin 9h, and material benzenemethanol inlet temperature is 30 DEG C, and the mass space velocity of its purification is 1h
-1, when parallel two towers, the charging of one of them tower accounts for the 80wt% of charging methanol quality mark, and residue 20wt% enters another scavenging tower.
Under the operation steps and operational condition of the present embodiment, basic nitrogen compound decreasing ratio in its methyl alcohol is 98%, outlet basic nitrogen compound content is 12 ~ 20ppm, methyl alcohol after purification is used for MTG produce, use the GSK-10 type MTG catalyzer of rope company of Top exploitation, and be 320 DEG C in import methanol feedstock temperature, reaction pressure is 1.8MPa, and methanol quality air speed is 1.0h
-1condition under react, its MTG catalyzer single run time average reaches 20 days, the regeneration period 20 times, the total treatment capacity of unit catalyst 12000 tons of methyl alcohol/ton catalyzer.
Claims (18)
1. a purification process for methanol conversion gasoline process Raw methyl alcohol, is characterized in that comprising the steps:
(1) acidic resins are loaded in 1# scavenging tower and 2# scavenging tower, first salt solution is conveyed in 1# and 2# scavenging tower from top, after soaking acidic resins, salt solution is put only, and by de-salted water to the acidic resins rinsed clean in scavenging tower, then dilute hydrochloric acid solution is conveyed in 1# and 2# scavenging tower from top, after soaking acidic resins, hydrochloric acid soln is put only, and by de-salted water by the acidic resins rinsed clean in scavenging tower, finally nitrogen is sent in two scavenging tower from bottom, and the outlet nitrogen of discharging from top of tower is sent to torch, purge totally until the free-water in acidic resins, complete the pre-treatment of acidic resins,
(2) when the basic nitrogen compound content in methanol feedstock is lower than 700ppm, material benzenemethanol is sent in 1# and 2# scavenging tower from top parallel connection and purifies, by adjusting the flow of two scavenging tower charging methyl alcohol, 70 ~ 90wt% of charging methanol quality mark is made to enter 1# scavenging tower, and remaining 10 ~ 30wt% enters 2# scavenging tower, the methyl alcohol after purification is sent to synthetic oil system after merging;
(3) along with the carrying out of methanol purification, when 1# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve of 1# scavenging tower, and the acidic resins changed in 1# scavenging tower, and charging methyl alcohol all enters 2# scavenging tower purifies, purifying methanol is sent to synthetic oil system;
(4) after the acidic resins of 1# scavenging tower load, according to step (1), pre-treatment is carried out to the resin in 1# scavenging tower, by the opening and closing of adjustment valve after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 2# scavenging tower, and remaining 50wt% enters 1# scavenging tower, when 2# scavenging tower outlet methyl alcohol neutral and alkali amount of nitrides being detected more than 20ppm, then close the input and output material valve of 2# scavenging tower, and the acidic resins changed in 2# scavenging tower, and charging methyl alcohol all enters 1# scavenging tower purifies, purifying methanol is sent to synthetic oil system,
(5) after the acidic resins of 2# scavenging tower load, according to step (1), pre-treatment is carried out to the resin in 2# scavenging tower, by the opening and closing of adjustment valve after being disposed, switch to parallel two towers feed state, and make the 50wt% of charging methanol quality mark enter 1# scavenging tower, and remaining 50wt% enters 2# scavenging tower, the methyl alcohol after purification is sent to synthetic oil system after merging;
(6) repeating step (3) ~ (5) namely realize when the continuous purification of methyl alcohol neutral and alkali amount of nitrides lower than methyl alcohol during 700ppm operates;
(7) as two scavenging tower be all in cleansing operation time, when the content >=700ppm of the basic nitrogen compound in material benzenemethanol being detected, then by the opening and closing of adjustment valve, rapidly purification system is switched to cascade towers state, ensure whole charging methyl alcohol all by after two scavenging tower series connection purifications, just can be sent to synthetic oil system;
(8) when any one scavenging tower is in acidic resins filling or regenerative process, and when the content >=700ppm of the basic nitrogen compound in material benzenemethanol being detected, then by the opening and closing of adjustment valve, part methyl alcohol is back to after scavenging tower tower top mixes with fresh methanol to carry out secondary-cleaned, ensure the purity of outlet methyl alcohol.
2. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that described is saturated aqueous common salt for the pretreated salt solution of acidic resins.
3. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that the time of described salt solution immersion acidic resins is 15 ~ 24h.
4. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that the described mass concentration for the pretreated dilute hydrochloric acid solution of acidic resins is 1 ~ 8wt%.
5. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that the time of described dilute hydrochloric acid solution immersion acidic resins is 2 ~ 10h.
6. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that the feeding temperature of described material benzenemethanol is 20 ~ 60 DEG C.
7. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 6, is characterized in that the feeding temperature of described material benzenemethanol is 30 ~ 50 DEG C.
8. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that described acidic resins are CT151 type or the C100E type of drift Lai Te (China) company; The D113 type that Chemical Plant of Nankai Univ. produces, D061 type or D152 type.
9. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, it is characterized in that the granularity of described acidic resins is 0.5 ~ 1.5mm, its coefficient of uniformity is 1.5 ~ 2.
10. the purification process of a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that described methyl alcohol is 1 ~ 30h through the mass space velocity that acidic resins exchange
-1.
The purification process of 11. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 10, is characterized in that described methyl alcohol is 10 ~ 20h through the mass space velocity that acidic resins exchange
-1.
The purification process of 12. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, all arranges safety valve described in it is characterized in that in two scavenging tower inlet line.
The purification process of 13. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 1, is characterized in that the methyl alcohol neutral and alkali nitride removal rate after described purification reaches 94 ~ 98%, outlet methyl alcohol neutral and alkali amount of nitrides≤20ppm.
The scavenging tower that the purification process of 14. a kind of methanol conversion gasoline process Raw methyl alcohol as described in any one of claim 1-13 uses, it comprises housing (1) to it is characterized in that scavenging tower, upper strata wire gauzee filter (2), acidic resins (3), back up pad (4), nitrogen sparger (5), nitrogen inlet tube (6), liquid-phase outlet pipe (7), nitrogen sprayer head (8), lower floor's wire gauzee filter (9), liquid phase shower nozzle (10), fluid inlet pipe (11), nitrogen outlet pipe (12), housing (1) is by upper cover, middle cylinder and lower cover composition, nitrogen outlet pipe (12) is arranged at upper cover top, liquid phase shower nozzle (10) is equipped with in upper cover inside, upper cover has fluid inlet pipe (11), liquid phase shower nozzle (10) is connected with fluid inlet pipe (11), back up pad (4), lower floor's wire gauzee filter (9), acidic resins (3) and upper strata wire gauzee filter (2) is followed successively by from down to up in middle cylinder, conical nitrogen sparger (5) is equipped with in lower cover inside, there is liquid phase vent pipe (7) lower cover bottom, nitrogen inlet tube (6) is had in liquid phase vent pipe (7) inside, there is nitrogen sprayer head (8) on nitrogen inlet tube (6) top, and nitrogen sprayer head (8) is positioned at conical nitrogen sparger (5).
The scavenging tower of the purification process use of 15. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 14, is characterized in that the aspect ratio of described middle cylinder is 3 ~ 10.
The scavenging tower of the purification process use of 16. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 14, is characterized in that the described loading height of acidic resins (3) and the ratio of middle cylinder height are 0.85 ~ 0.92.
The scavenging tower of the purification process use of 17. a kind of methanol conversion gasoline process Raw methyl alcohol as claimed in claim 14, is characterized in that described nitrogen sprayer head (8) is upper end closed surrounding hollow out.
The scavenging tower that the purification process of 18. a kind of methanol conversion gasoline process Raw methyl alcohol as described in claim .14 uses, is characterized in that described upper strata wire gauzee filter (2) is portable.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510016206.8A CN104591962B (en) | 2015-01-13 | 2015-01-13 | The purification process of methanol conversion gasoline process Raw methyl alcohol and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510016206.8A CN104591962B (en) | 2015-01-13 | 2015-01-13 | The purification process of methanol conversion gasoline process Raw methyl alcohol and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104591962A true CN104591962A (en) | 2015-05-06 |
| CN104591962B CN104591962B (en) | 2016-02-24 |
Family
ID=53118073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510016206.8A Expired - Fee Related CN104591962B (en) | 2015-01-13 | 2015-01-13 | The purification process of methanol conversion gasoline process Raw methyl alcohol and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104591962B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106883099A (en) * | 2017-02-20 | 2017-06-23 | 新能（廊坊）能源化工技术服务有限公司 | MTO grades of methanol production system and production method |
| CN107774008A (en) * | 2016-08-26 | 2018-03-09 | 中国石油化工股份有限公司 | The apparatus and method that a kind of physical absorption improves UV transmittance of ethylene glycol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157374A (en) * | 1992-11-26 | 1994-06-03 | Mitsubishi Gas Chem Co Inc | Purification of methanol and its equipment |
| CN2782678Y (en) * | 2005-03-28 | 2006-05-24 | 郭钦才 | Methanol purifying tower |
| CN102659568A (en) * | 2012-05-03 | 2012-09-12 | 中粮生物化学（安徽）股份有限公司 | Method for continuously removing cations out of solution containing citric acid |
-
2015
- 2015-01-13 CN CN201510016206.8A patent/CN104591962B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06157374A (en) * | 1992-11-26 | 1994-06-03 | Mitsubishi Gas Chem Co Inc | Purification of methanol and its equipment |
| CN2782678Y (en) * | 2005-03-28 | 2006-05-24 | 郭钦才 | Methanol purifying tower |
| CN102659568A (en) * | 2012-05-03 | 2012-09-12 | 中粮生物化学（安徽）股份有限公司 | Method for continuously removing cations out of solution containing citric acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107774008A (en) * | 2016-08-26 | 2018-03-09 | 中国石油化工股份有限公司 | The apparatus and method that a kind of physical absorption improves UV transmittance of ethylene glycol |
| CN106883099A (en) * | 2017-02-20 | 2017-06-23 | 新能（廊坊）能源化工技术服务有限公司 | MTO grades of methanol production system and production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104591962B (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105457570B (en) | The coaxial-type two-stage regeneration reaction unit and its reaction method of methanol or dimethyl ether conversion producing light olefins and aromatic hydrocarbons | |
| CN101274878B (en) | Fluidized catalyzing method for producing dimethyl ether by methanol multi-stage gas phase dehydration | |
| CN102320910B (en) | Crude benzene hydrogenation method | |
| CN103449951A (en) | Butane dehydrogenation process technology | |
| CN101574622A (en) | Dry-method desulphurization and deodorization technology with high efficiency low pressure drop | |
| CN111320528A (en) | Method and system for preparing ethanol by comprehensively utilizing steel mill tail gas | |
| CN103772125A (en) | Method for preparing ethylbenzene by using refinery dry gas as raw material | |
| CN104591962B (en) | The purification process of methanol conversion gasoline process Raw methyl alcohol and device | |
| CN101757943B (en) | Catalyst for synthesizing methanol by hydrogenating carbon dioxide, preparation method and application thereof | |
| CN201161998Y (en) | Petroleum hydrocarbon raw materials catalytic conversion reaction-regeneration apparatus | |
| CN101928598B (en) | Method and system for producing gasoline and propylene by integrating heavy oil catalytic cracking with oxygen-containing compound conversion | |
| CN104496754B (en) | A kind of purifying method for methanol conversion gasoline Raw methyl alcohol and equipment | |
| CN204981386U (en) | Rapid cooling washing system among methyl alcohol system olefin device | |
| CN104557415A (en) | System and method for preparing aromatic hydrocarbon and coproducing liquefied gas by converting methanol and/or dimethyl ether | |
| CN104496755B (en) | A kind of purification process for methanol conversion gasoline Raw methyl alcohol | |
| CN104987895A (en) | Desulfuration regeneration tower | |
| CN104610026A (en) | Method and system for producing polyoxymethylene dimethyl ethers (DMMn) through dual reactor | |
| CN101708822A (en) | Method and device for removing liquid and solid of continuous reformed hydrogen | |
| CN113528196B (en) | Shifted gas treatment or improvement process and low-temperature methanol washing device and process | |
| CN104098069A (en) | New process for extraction of hydrogen from coal gas | |
| CN102924214A (en) | Production technique of propylene | |
| CN206955651U (en) | A kind of system for reclaiming oil refinery waste hydrogen and being used for chemical fertilizer factory's synthetic ammonia installation | |
| CN104987274A (en) | System for preparing low carbon olefin from coal-based methanol | |
| CN206706024U (en) | A kind of hydrocracking unit | |
| CN101987722A (en) | Hydrofined gas on-line desulfurization and utilization process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160224 Termination date: 20190113 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |