CN100471825C - Technology of preparing hydrocarbons produce from methanol by one-step method - Google Patents
Technology of preparing hydrocarbons produce from methanol by one-step method Download PDFInfo
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- CN100471825C CN100471825C CN 200610048298 CN200610048298A CN100471825C CN 100471825 C CN100471825 C CN 100471825C CN 200610048298 CN200610048298 CN 200610048298 CN 200610048298 A CN200610048298 A CN 200610048298A CN 100471825 C CN100471825 C CN 100471825C
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Abstract
The invention discloses a preparing method of hydrocarbon based on once carbinol, which comprises the following steps: heating carbinol to reacting temperature; entering into the reactor with acid siallite zeolite molecular sieve catalyst; transmitting into hydrocarbon compound at 300-500 deg.c under 0.1-5.0 Mpa with the speed at 0.1-10.0h-1; cooling; separating the C5+ hydrocarbon product and gas phase part; entering gas phase in the compressor; making partial liquid leave system; adopting others as circulating material to blend with raw carbinol; returning to reactor to proceed next reaction.
Description
Technical field
The present invention relates to a kind of methanol by one-step method and transform the method for producing hydrocarbon products,
Technical background
International Crude Oil continues to raise at present, and one of them important factor is exactly because the arrival of predictable oil production summit causes substitute energy Study on Technology upsurge in the international coverage thus.The feature of China's energy structure is rich coal, weak breath, oil starvation, therefore, for China, considers from the energy security strategic angle that the demand of development substitute energy is more urgent.
Methyl alcohol is the foundation stone of petrochemical complex, and by suitable catalytic process, methyl alcohol can be converted into the multiple product of petrochemical complex, as the mixture of ethene, propylene, aromatic hydrocarbons, alkane and the said products.
Methanol conversion system gasoline (MTG) technology is a kind of methanol conversion technology by the invention of Mobil company.From 1974, the said firm applied for the patent of multinomial relevant methanol conversion system gasoline, and in the eighties at the device that New Zealand has built plant-scale methanol conversion system gasoline, successfully carried out commerce for many years and turned round.
Yet the technology of the methanol conversion system hydrocarbon products in past adopts two sections conversion process mostly.United States Patent (USP) 3931349 is patents of the methanol conversion system hydro carbons of Mobil company alerting bulletin, adopt two sections conversion process of fixed bed, wherein first section reaction is dimethyl ether by methanol dehydration, the one section outlet material, the mixture that comprises methyl alcohol, dme and water, enter second stage reactor, under the effect of molecular sieve catalyst, generate gasoline fraction section product.
4579999 of United States Patent (USP)s have been announced the technology of another two-stage method methanol conversion system gasoline fraction section hydrocarbon products, load molecular sieve catalyst in the one section reactor, and methyl alcohol at first is converted into low-carbon alkene and portion C
5 +Hydrocarbon is with C
5 +After the refrigerated separation, low-carbon alkene enters second stage reactor, under the effect of olefin polymerization catalysis, further transforms and generates gasoline fraction section product.
United States Patent (USP) 4689205 has announced that a kind of methanol multi-stage transforms the technology of producing hydrocarbon.The technology that this patent is announced is similar substantially to United States Patent (USP) 4579999, and in first stage reactor, methyl alcohol is converted into C under certain temperature and pressure condition
2～C
1Alkene and portion C
5 -Hydrocarbon is with C
5 +After hydrocarbon separated, remainder entered second section reactor, adopted olefin polymerization catalysis, the low-carbon alkene of first section reaction generation further was polymerized to the hydrocarbon product of gasoline fraction.Different is, in the technology that this patent is announced, first section employing be fluidized-bed reactor.
No matter adopt fixed bed or fluidized-bed reactor, the technology of two-stage method preparing hydrocarbon products by methanol conversion all exists technical process long, and reactor quantity is many, invests big shortcoming.
Summary of the invention
The objective of the invention is at the problems referred to above, the technology of the one-stage process preparing hydrocarbon products by methanol conversion that a kind of technical process is simple, investment is little is provided.
The process using fixed-bed reactor of single stage method preparing hydrocarbon products by methanol conversion provided by the invention, catalyzer is the acid Si-Al zeolite molecular sieve catalyst of synthetic, under the effect of above-mentioned catalyzer, methyl alcohol is through intermolecular or intramolecular dehydration, generate intermediate compounds such as methylene radical or dme, reactions such as carbochain growth, cyclisation, polymerization further take place in these compounds under the acidic zeolite surface action, finally generate C
1～C
12Hydrocarbon products.
Preparing hydrocarbons produce from methanol by one-step method technology provided by the invention comprises the steps:
(1), material benzenemethanol is heated to temperature of reaction, enter in the methanol conversion that acid Si-Al zeolite molecular sieve catalyst is housed, at 300～500 ℃, 0.1～5.0MPa, the liquid air speed of methyl alcohol is 0.1～10.0h
-1Under the condition, be converted into the hydrocarbon products mixture;
(2), reaction generates in the methanol conversion hydrocarbon products mixture carries out refrigerated separation, liquid portion is for being C
5 +Hydrocarbon products and gas phase part;
(3), gas phase partly enters recycle compressor, a liquid part that obtains after the compression is left system as liquefied petroleum gas (LPG) (LPG) product, another part mixes with material benzenemethanol as recycle stock, further reacts in the Returning reactor;
(4), for keeping system stability, in the gas-phase product that obtains after the gas-liquid separation, a part is used as off-gas and is discharged into outside the system.
Aforesaid material benzenemethanol can be by any carbonaceous material such as coal, Sweet natural gas, biomass etc. for raw material is synthesized into, material benzenemethanol both can be a refined methanol, also can be thick methyl alcohol, the methanol content of thick methyl alcohol is preferably in more than 70%.
Aforesaid catalyzer is commercially available acid Si-Al zeolite molecular sieve catalyst, as ZSM-5, ZSM-11, ZSM-48 etc., wherein be preferably the ZSM-5 molecular sieve catalyst, optimal is to be made by following synthetic method at the special molecular sieve catalyst of developing of single stage method methanol conversion system hydrocarbon products technology:
(1) directed agents synthetic (referring to Chinese patent 00109593.5):
Silicon source and deionized water, template are configured to A solution, aluminium source, mineral acid and deionized water are configured to B solution, A solution is put into synthesis reactor and is stirred, and under 200-400 rev/min of stirring, the B drips of solution is added in the A solution then, still is airtight, continue stirring and begin after 10-20 minute to heat up, be warming up to 120 ℃ of constant temperature 20-25 hours, be warming up to 165-170 ℃ with 10-15 ℃/hour again by the speed of room temperature with 2-5 ℃/minute, cool, make directed agents in the airtight bottle of packing into;
Wherein the mol ratio of each component is
SiO
2: Al
2O
3: Na
2O: template: mineral acid: H
2O=
40—80：1：7—15：25—40：3.0-7.5：2000—4000；
(2) molecular sieve is synthetic:
With silicon source and directed agents, deionized water is configured to C solution, the aluminium source, mineral acid and ionized water are configured to D solution, solubility lanthanum salt is made the solution of 0.1-1.0Mol/L, be designated as E solution, C solution is put into synthesis reactor, beginning is stirred with 200-400 rev/min speed, again E solution is added, add the directed agents that accounts for cumulative volume 5-10% then, be warming up to 50-80 ℃ with 3-5 ℃/minutes speed, at last the D drips of solution is added in the still, still is airtight, continue to stir and to begin after 10-20 minute to heat up, be warming up to 120 ℃ by room temperature with 2-5 ℃/minute speed, constant temperature 20-25 hour, with 10-15 ℃/hour be warming up to 155-165 ℃, constant temperature 20-25 hours cools off then again, cooling, material is drawn off, precipitation, filter, filter cake is washed till the solution pH value is 7-8, through 110-120 ℃ of oven dry, in 520-540 ℃ of following roastings 3-5 hours, obtain the LaZSM-5 molecular sieve;
The mol ratio of aforesaid each component is:
SiO
2: Al
2O
3: Na
2O:R-NH
3: mineral acid: La
3+: H
2O=
40—80：1：7—15：25—40：3.0-7.5：0.1—2.0：2000—4000；
(3) preparation catalyzer
The acid solution of LaZSM-5 molecular sieve process 0.5-1Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) % behind oven dry, the 500-540 ℃ roasting 3-5 hour, obtains the LaHZSM-5 molecular sieve then.Weight percent 100-50:0-50 adding binding agent by LaHZSM-5 molecular sieve and binding agent mixes then, uses the dilute nitric acid solution kneading and compacting of volumetric concentration＜5% simultaneously, after the oven dry, makes catalyzer after 500-540 ℃ of roasting 3-5 hour.
Aforesaid silicon source is silicon-containing materials such as water glass, tetraethoxysilance, white carbon black, silicon sol.
Aforesaid aluminium source is aluminum soluble salts such as Tai-Ace S 150, aluminum nitrate.
Aforesaid template is organic amines such as n-Butyl Amine 99, quadrol, 1,6 hexanediamine, ethamine.
Aforesaid mineral acid be sulfuric acid, nitric acid, hydrochloric acid, etc. mineral acid.
Aforesaid mineral alkali is sodium hydroxide, yellow soda ash etc.
Aforesaid binding agent is aluminum oxide, diatomite, boehmite, silicon-dioxide equimolecular sieve moulding binding agent commonly used.
In the processing step 3 of the present invention, the process that methanol conversion generates hydrocarbon is thermopositive reaction, revolution 1kg methyl alcohol, approximately emit the heat of 1.74MJ, if do not take corresponding heat to shift out measure, then bed temperature causes reaction normally to carry out with out of hand, simultaneously too high temperature also can accelerator activator the coking and deactivation process, thereby make the catalyzer one way lost of life.Circulate by recycle stock, material benzenemethanol is diluted, can alleviate the heat effect of reaction process.Simultaneously, under the effect of special-purpose ZSM-5 molecular sieve catalyst, the alkene in the recycle stock can also further react, and generates C
5 +Hydrocarbon products reaches and improves C
5 +The purpose of hydrocarbon products yield.
For reaching the purpose of control methanol conversion temperature rise, the mass ratio of recycle stock and methyl alcohol should be 5～25 in the step 3, is preferably 10～20.
The present invention compared with prior art has following advantage:
Technology provided by the invention is carried out the single stage method preparing hydrocarbon products by methanol conversion, has the technical process weak point, and is simple to operate, the advantage of reduced investment.
Description of drawings
Fig. 1 is a process flow diagram of the present invention
As shown in the figure, the 1st, methyl alcohol storage tank, the 2nd, volume pump, the 3rd, methanol conversion, the 4th, cooling separation, the 5th, recycle compressor, the 6th, off-gas, the 7th, C
5 +Hydrocarbon product, the 8th, the LPG product
Embodiment
A. directed agents is synthetic
The mol ratio of directed agents consists of SiO
2: Al
2O
3: Na
2O: n-Butyl Amine 99: H
2SO
1: H
2O=40:1:10:28:7.2:2800.The silicon source is adopted and is consisted of: SiO
2=25.130
0Na
2O=8.12%; H
2The water glass of O=66.75% at first takes by weighing 600 gram water glass, adds the n-Butyl Amine 99 of 126.5 grams and the deionized water of 1181.3 grams and makes A solution, pack in the synthesis reactor,, under 300 rev/mins stirring, stir, take by weighing the Tai-Ace S 150 of 41.82 grams again, insert in the beaker that 1561.4 gram water are housed, add the sulfuric acid of 15.8 grams then, stir, make B solution it is dropped in the solution in the still with glass stick, then that still is airtight, continue stirring and begin after 10-20 minute to heat up.The first step was warming up to 120 ℃ of constant temperature 20 hours by room temperature with 2 ℃/minute speed, second step, be warming up to 165 ℃ with 10 ℃/hour speed again after, the cooling cooling draws off material in the air-tight bottle of packing into.
B. molecular sieve is synthetic
It is composed as follows to prepare burden: SiO
2: Al
2O
3: Na
2O: directed agents: H
2SO
4: lanthanum nitrate: H
2O=20:1:7:2:0.5:0.1:2500;
The silicon source is adopted and is consisted of: SiO
2=25.13%; Na
2O=8.12%; H
2The water glass of O=66.75%, at first take by weighing 500 gram water glass, the deionized water that adds 1548.75 grams then, make C solution, put it in the synthesis reactor and stir, beginning is stirred with 200-400 rev/min speed, the lanthanum nitrate hexahydrate 10ml of measuring 0.1Mol/L again adds in the still as E solution, add the directed agents 180ml that accounts for cumulative volume 5-10% then, be warming up to 80 ℃ with 5 ℃/minute speed, and then the Tai-Ace S 150 that take by weighing 69.6 grams add the sulfuric acid that the deionized waters and 4.8 of 2218.3 grams restrain and be configured to D solution, it is dropped in the still in the solution, then that still is airtight, continue stirring and begin after 10 minutes to heat up.The first step, be warming up to 120 ℃ of constant temperature 25 hours with 3 ℃/minute speed, second step, again with 10 ℃/hour be warming up to 160 ℃ of constant temperature at a slow speed 20-25 hours, after adopting cooling water temperature then, material is drawn off, and sedimentation and filtration is washed till pH value with material solution and is 8, is placed in the stove through 110 ℃ of oven dry and is the LaZSM-5 molecular screen primary powder in 5 hours in 540 ℃ of following roastings.
C. Preparation of Catalyst
The hydrochloric acid soln of above-mentioned molecular sieve process 0.5Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) %, oven dry, 500 ℃ of roastings obtained the LaHZSM-5 molecular sieve after 3 hours then.Weight percent by LaHZSM-5 molecular sieve and binding agent is that 50:50 adding binding agent mixes then, uses the dilute nitric acid solution kneading and compacting of volumetric concentration 2% simultaneously, after the oven dry, makes catalyzer 500 ℃ of roastings after 4 hours.
As the accompanying drawing flow process, methanol conversion is a stainless steel tubulation formula reactor, interior dress HZSM-5 catalyzer 5L, heavy 3.05kg.
The methanol conversion process condition is: reaction inlet temperature T=320 ℃, inlet pressure P=2.0Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=1.4h
-1Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
A. directed agents is synthetic
The raw material of directed agents consists of SiO
2: Al
2O
3: Na
2O:1.6-hexanediamine: H
2SO
4: H
2O=60:1:13:32:3.3:3000.The silicon source is adopted and is consisted of: SiO
2=25.13%; Na
2O=8.12%; H
2The water glass of O=66.75%, at first take by weighing 600 gram water glass, add the deionized waters of 728.9 grams and 149.9 grams 1, the 6-hexanediamine makes A solution and packs in the synthesis reactor, stirs under 300 rev/mins stirring, takes by weighing the aluminum nitrates of 17.93 grams again, insert in the beaker that 1561.4 gram water are housed, the sulfuric acid that add 15.6 grams then stir with glass stick and to make B solution, and it is dropped in the solution in the still, then that still is airtight, continue stirring and begin after 10-20 minute to heat up.The first step was warming up to 120 ℃ of constant temperature 20 hours by room temperature with 2 ℃/minute speed, second step, be warming up to 165 ℃ with 10 ℃/hour speed again, and cool, draw off in the air-tight bottle of packing into material stand-by.
B. molecular sieve is synthetic
It is composed as follows to prepare burden: SiO
2: Al
2O
3: Na
2O: directed agents: HNO
3: lanthanum sulfat:
+H
2O=40:1:10:3:2.1:0.5:2800;
The silicon source is adopted and is consisted of: SiO
2=25.23%; H
2The silicon sol of O=74.75%, at first take by weighing 600 gram silicon sol, the deionized water that adds 16.73 gram sodium hydroxide and 1156.3 grams is then made C solution, putting into synthesis reactor stirs, the lanthanum sulfat solution 65ml of measuring 0.5Mol/L again adds in the still as E solution, add the directed agents 189ml that accounts for cumulative volume 5-10% then, be warming up to 70 ℃ with 3 ℃/minute speed, and then the Tai-Ace S 150 that takes by weighing 41.8 grams adds the deionized water of 1565.2 grams and the nitric acid of 15.8 grams is configured to D solution, then under 200 rev/mins of stirrings, it is dropped in the still in the solution, then that still is airtight, continue to stir and begin after 20 minutes to heat up.The first step, be warming up to 120 ℃ of constant temperature 20 hours with 3 ℃/minute speed, second step, again with 10 ℃/hour be warming up to 165 ℃ of constant temperature at a slow speed 20 hours, adopt cooling water temperature then, material is drawn off, washing of precipitate, make solution be washed till pH value and be 7, be placed in the stove through 120 ℃ of oven dry and be the LaZSM-5 molecular screen primary powder in 3 hours in 540 ℃ of following roastings.
C. Preparation of Catalyst
The sulfuric acid solution liquid of above-mentioned molecular sieve process 0.8Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) %, oven dry, 520 ℃ of roastings obtained the LaHZSM-5 molecular sieve after 5 hours then.Weight ratio 60:40 adding binding agent by LaHZSM-5 molecular sieve and boehmite mixes then, uses the dilute nitric acid solution kneading and compacting of volumetric concentration 3% simultaneously, after the oven dry, makes catalyzer 540 ℃ of roastings after 5 hours.
With embodiment 1, the mass ratio of recycle stock and material benzenemethanol is 15, the identical embodiment 1 of other conditions, reaction result see Table 1, products distribution sees Table 2.
Embodiment 3
A. directed agents is synthetic
The raw material of directed agents consists of SiO
2: Al
2O
3: Na
2O: ethamine: H
2SO
4: H
2O=80:1:15:38:5.2:3800
The silicon source is adopted and is consisted of: SiO
2=25.13%; Na
2O=8.12%; H
2The water glass of O=66.75%, at first take by weighing 600 gram water glass, add the ethamine of 84.33 grams and the deionized water of 1181.3 grams and make A solution, in the synthesis reactor of packing into, under 300 rev/mins stirring, stir, take by weighing the Tai-Ace S 150 of 41.82 grams again, insert in the beaker that 1561.4 gram water are housed, add the sulfuric acid of 15.8 grams then, stir with glass stick and to make B solution, it is dropped in the solution in the still, then that still is airtight, continue to stir and begin after 10-20 minute to heat up.The first step was warming up to 120 ℃ of constant temperature 20 hours by room temperature with 2 ℃/minute speed, second step, and be warming up to 165 ℃ with 10 ℃/hour speed again and cool, material is drawn off in the air-tight bottle of packing into.
B. molecular sieve is synthetic
It is composed as follows to prepare burden: SiO
2: Al
2O
3: Na
2O: directed agents: HCl: lanthanum sulfat: H
2O=60:1:12:4:5.7:2.0:3000,
The silicon source is adopted and is consisted of: SiO
2=25.13%; Na
2O=8.12%; H
2The water glass of O=66.75%, at first take by weighing 600 gram water glass, 728.4 gram deionized waters are made C solution then, putting into synthesis reactor stirs, and then measure the directed agents 184ml that accounts for cumulative volume 8% and add, the lanthanum sulfat solution 41.5ml of measuring 2.0Mol/L again adds in the still as E solution, add directed agents 189ml then, be warming up to 65 ℃ with 3 ℃/minute speed, the aluminum nitrates that take by weighing 15.71 grams again add the phosphorylated ligands that the deionized waters and 28.1 of 1115.6 grams restrain and are set to D solution, then under 250 rev/mins of stirrings, it is dropped in the still in the solution, the amount of last D3 is that then that still is airtight, continuation is stirred and begun after 15 minutes to heat up.At first be warming up to 120 ℃ of constant temperature 25 hours with 5 ℃/minute speed, second step, again with 10 ℃/hour be warming up to 165 ℃ of constant temperature at a slow speed 20 hours, adopt cooling water temperature then, material is drawn off, sedimentation and filtration is washed till pH value with solution again and is 8, is placed in the stove through 110 ℃ of oven dry and obtains the LaZSM-5 molecular screen primary powder in 5 hours in 540 ℃ of following roastings.
C. Preparation of Catalyst
The salpeter solution of above-mentioned molecular sieve process 1Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) %, oven dry, 540 ℃ of roastings obtained the LaHZSM-5 molecular sieve after 5 hours then.Add binding agent by LaHZSM-5 molecular sieve and diatomaceous weight percent 80:20 then and mix, use the dilute nitric acid solution kneading and compacting of volumetric concentration 4% simultaneously, after the oven dry, make catalyzer after 5 hours 540 ℃ of roastings.
With embodiment 1, be raw material with thick methyl alcohol, the methanol content of thick methanol feedstock is 80%, all the other are water, the identical embodiment 1 of other conditions, the gained reaction result sees Table 1, and products distribution sees Table 2.
A. directed agents adopts institute's synthetic directed agents among the embodiment 1.
B. molecular sieve is synthetic
It is composed as follows to prepare burden: SiO
2: Al
2O
3: Na
2O: directed agents: HNO
3: lanthanum nitrate: H
2O=80:1:12:2::8.3:1.0:3800,
Silicon source employing group SiO
2Content is 99.8% white carbon black, at first take by weighing 151.1 gram white carbon blacks, insert in 1072.9 deionized waters that restrain and make C solution, the lanthanum nitrate hexahydrate 31ml of measuring 1.0Mol/L again adds in the still as E solution, add directed agents 138ml then, be warming up to 70 ℃ with 5 ℃/minute speed, and then the Tai-Ace S 150 that takes by weighing 20.9 grams adds the deionized water of 1062.7 grams and the nitric acid of 25.0 grams is configured to D solution, under 300 rev/mins stirring, it is dropped in the still in the solution, then that still is airtight, continue stirring and begin after 10 minutes to heat up.The first step, rise to 120 ℃ of constant temperature 20 hours by room temperature with 4 ℃/minute speed, second step, again with 10 ℃/hour rise to 160 ℃ of constant temperature 25 hours at a slow speed, adopt cooling water temperature then, material is drawn off, and washing of precipitate makes the material solution pH value be 8, is placed in the stove through 110 ℃ of oven dry and is the LaZSM-5 molecular screen primary powder in 3 hours in 540 ℃ of following roastings.
C. prepare catalyzer
The hydrochloric acid acid solution of above-mentioned molecular sieve process 0.8Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) %, oven dry, 540 ℃ of roastings obtained the LaHZSM-5 molecular sieve after 3 hours then.Directly with after the oven dry of LaHZSM-5 molecular sieve compressing tablet, make catalyzer after 3 hours then 540 ℃ of roastings.
With embodiment 1, the methanol conversion process condition is: reaction inlet temperature T=320 ℃, inlet pressure P=1.0Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=1.4h-1.Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
A. directed agents adopts institute's synthetic directed agents among the embodiment 3.
B. molecular sieve is synthetic
It is composed as follows to prepare burden: SiO
2: Al
2O
3: Na
2O: directed agents: H
2SO
4: lanthanum sulfat: H
2O=100:1:14:3:2.4:0.8:4000,
It is 28.0% tetraethoxysilance that content is adopted in the silicon source, at first take by weighing 1867.25 gram tetraethoxysilances, the deionized water of 460.3 grams is made C solution then, putting into synthesis reactor stirs, measuring directed agents 198ml then earlier adds, the lanthanum sulfat solution 78ml of measuring 1.0Mol/L again adds in the still as E solution, be warming up to 70 ℃ with 3 ℃/minute speed, and then the Tai-Ace S 150 that takes by weighing 27.9 grams adds the deionized water of 1193.8 grams and the hydrochloric acid of 21.2 grams is configured to D solution, then under 400 rev/mins of stirrings, it is dropped in the still in the solution, then that still is airtight, continue to stir and begin after 10 minutes to heat up.At first be warming up to 120 ℃ of constant temperature 20 hours with 3 ℃/minute speed, second step, again with 10 ℃/hour be warming up to 160 ℃ of constant temperature at a slow speed 25 hours, adopt cooling water temperature then, material is drawn off, washing of precipitate makes solution be washed till pH value to be 8, to be placed in the stove through 110 ℃ of oven dry and to be the LaZSM-5 molecular screen primary powder in 4 hours in 540 ℃ of following roastings.
C. prepare catalyzer
The sulphuric acid soln of above-mentioned molecular sieve process 1Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1 (m) %, oven dry, 510 ℃ of roastings obtained the LaHZSM-5 molecular sieve after 4 hours then.Weight percent 60:40 adding binding agent by LaHZSM-5 molecular sieve and binding agent mixes then, uses the dilute nitric acid solution kneading and compacting of volumetric concentration 2% simultaneously, after the oven dry, makes catalyzer 520 ℃ of roastings after 3 hours.
With embodiment 1, the methanol conversion process condition is: reaction inlet temperature T=320 ℃, inlet pressure P=2.0Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=5h
-1Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
Catalyzer adopts commercially available HZSM-5 molecular sieve, and silica alumina ratio is 50, adds binding agent by the weight percent 70:30 of HZSM-5 molecular sieve and binding agent and mixes, and also promptly claims 70 mol sieve to restrain boehmites with 30, mixes.Use the dilute nitric acid solution kneading and compacting of volumetric concentration 2% again, after the oven dry, make catalyzer after 3 hours 520 ℃ of roastings.
With embodiment 1, the methanol conversion process condition is: reaction inlet temperature T=320 ℃, inlet pressure P=0.4Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=1.4h
-1Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
Catalyzer is selected commercially available HZSM-11 molecular sieve for use, and silica alumina ratio is that the 48 weight percent 70:30 adding binding agents by HZSM-11 molecular sieve and binding agent mix, and also promptly claims 70 mol sieve and 30 gram boehmites, mixes.Use the dilute nitric acid solution kneading and compacting of volumetric concentration 2% again, after the oven dry, make catalyzer after 3 hours 540 ℃ of roastings.
With embodiment 1, the methanol conversion process condition is: reaction inlet temperature T=400 ℃, inlet pressure P=1.0Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=1.4h
-1Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
Embodiment 8
Catalyzer is selected commercially available HZSM-48 molecular sieve for use, and silica alumina ratio is 55.Weight percent 70:30 adding binding agent by HZSM-48 molecular sieve and binding agent mixes, and also promptly claims 70 mol sieve and 30 gram boehmites, mixes.Use the dilute nitric acid solution kneading and compacting of volumetric concentration 2% again, after the oven dry, make catalyzer after 3 hours 540 ℃ of roastings.
With embodiment 1, the methanol conversion process condition is: reaction inlet temperature T=320 ℃, inlet pressure P=1.0Mpa, the employing refined methanol is a raw material, liquid air speed LHSV=1.4h
-1Recycle stock and material benzenemethanol mass ratio are 12.
Adopt above-mentioned processing condition, the reaction result of one-stage process preparing hydrocarbon products by methanol conversion sees Table 1, and products distribution sees Table 2.
Table 1 embodiment reaction result
Table 2. liquid phase hydro carbons products distribution
Claims (10)
1. the technology of a preparing hydrocarbons produce from methanol by one-step method is characterized in that comprising the steps:
(1), material benzenemethanol is heated to temperature of reaction, enter in the methanol conversion that acid Si-Al zeolite molecular sieve catalyst is housed, at 300～500 ℃, 0.1～5.0MPa, the liquid air speed of methyl alcohol is 0.1～10.0h
-1Under the condition, be converted into the hydrocarbon products mixture;
(2), the hydrocarbon products mixture that reaction generates in the methanol conversion carries out refrigerated separation, liquid portion C
5 +Hydrocarbon products and gas phase part;
(3), gas phase partly enters recycle compressor, a liquid part that obtains after the compression is left system as liquefied petroleum gas product, another part mixes with material benzenemethanol as recycle stock, further reacts in the Returning reactor;
(4), for keeping system stability, in the gas-phase product that obtains after the gas-liquid separation, a part is used as off-gas and is discharged into outside the system.
2, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 1, it is characterized in that described material benzenemethanol is is that raw material is synthesized into by coal, Sweet natural gas or biomass, material benzenemethanol is that refined methanol or methanol content are at thick methyl alcohol more than 70%.
3, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 1 is characterized in that described catalyzer is ZSM-5, ZSM-11, ZSM-48 or is made by following synthetic method:
(1) directed agents is synthetic:
Silicon source and deionized water, template are configured to A solution, aluminium source, mineral acid and deionized water are configured to B solution, A solution is put into synthesis reactor and is stirred, and under 200-400 rev/min of stirring, the B drips of solution is added in the A solution then, still is airtight, continue stirring and begin after 10-20 minute to heat up, be warming up to 120 ℃ of constant temperature 20-25 hours, be warming up to 165-170 ℃ with 10-15 ℃/hour again by the speed of room temperature with 2-5 ℃/minute, cool, make directed agents in the airtight bottle of packing into;
Wherein the mol ratio of each component is
SiO
2: Al
2O
3: Na
2O: template: mineral acid: H
2O=40-80:1:7-15:25-40:3.0-7.5:2000-4000;
(2) molecular sieve is synthetic:
With silicon source and directed agents, deionized water is configured to C solution, the aluminium source, mineral acid and ionized water are configured to D solution, solubility lanthanum salt is made the solution of 0.1-1.0Mol/L, be designated as E solution, C solution is put into synthesis reactor, beginning is stirred with 200-400 rev/min speed, again E solution is added, add the directed agents that accounts for cumulative volume 5-10% then, be warming up to 50-80 ℃ with 3-5 ℃/minutes speed, at last the D drips of solution is added in the still, still is airtight, continue to stir and to begin after 10-20 minute to heat up, be warming up to 120 ℃ by room temperature with 2-5 ℃/minute speed, constant temperature 20-25 hour, with 10-15 ℃/hour be warming up to 155-165 ℃, constant temperature 20-25 hours cools off then again, cooling, material is drawn off, precipitation, filter, filter cake is washed till the solution pH value is 7-8, through 110-120 ℃ of oven dry, in 520-540 ℃ of following roastings 3-5 hours, obtain the LaZSM-5 molecular sieve;
The mol ratio of aforesaid each component is:
SiO
2: Al
2O
3: Na
2O:R-NH
3: mineral acid: La
3+: H
2O=40-80:1:7-15:25-40:3.0-7.5:0.1-2.0:2000-4000;
(3) preparation catalyzer
The acid solution of LaZSM-5 molecular sieve process 0.5-1Mol/L is carried out ion-exchange, until the Na of LaZSM-5 molecular sieve
+Content＜0.1m%, then behind oven dry, the 500-540 ℃ roasting 3-5 hour, obtain the LaHZSM-5 molecular sieve, weight percent 100-50:0-50 adding binding agent by LaHZSM-5 molecular sieve and binding agent mixes then, use the dilute nitric acid solution kneading and compacting of volumetric concentration＜5% simultaneously, after the oven dry, after 500-540 ℃ of roasting 3-5 hour, make catalyzer.
4, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 3 is characterized in that described silicon source is water glass, tetraethoxysilance, white carbon black or silicon sol.
5, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 3 is characterized in that described aluminium source is Tai-Ace S 150 or aluminum nitrate.
6, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 3 is characterized in that described template is n-Butyl Amine 99, quadrol, 1,6 hexanediamine or ethamine.
7, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 3 is characterized in that described mineral acid is sulfuric acid, nitric acid or hydrochloric acid.
8, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 3 is characterized in that described binding agent is aluminum oxide, diatomite, boehmite or silicon-dioxide.
9, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 1, the mass ratio that it is characterized in that recycle stock and methyl alcohol is 5～25.
10, the technology of a kind of preparing hydrocarbons produce from methanol by one-step method as claimed in claim 9, the mass ratio that it is characterized in that described recycle stock and methyl alcohol is 10～20.
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| CN102618316B (en) * | 2012-03-12 | 2014-09-17 | 江苏煤化工程研究设计院有限公司 | Technique method for producing oil product and co-producing propylene by utilizing methyl alcohol and mixing fixed bed |
| CN103468299A (en) * | 2012-06-08 | 2013-12-25 | 渭南高新区爱心有限责任公司 | Dimethyl ether-to-gasoline process technology |
| CN103881748A (en) * | 2013-05-24 | 2014-06-25 | 洛阳市科创石化科技开发有限公司 | Technique method for producing gasoline by using methanol through one-step method |
| CN103865564B (en) * | 2014-02-24 | 2015-08-19 | 中国海洋石油总公司 | The integrated approach of a kind of methyl alcohol or DME synthesis gasoline |
| CN103865563A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Low-energy-consumption method for synthetising gasoline from methanol |
| CN103865562A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing gasoline from methanol |
| CN105312079A (en) * | 2014-05-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Coal-based/bio-based oxygen-containing compound conversion catalyst, preparation method and applications thereof |
| CN104130796A (en) * | 2014-08-27 | 2014-11-05 | 张永魁 | Technology for preparing high-cleanliness and high-octane gasoline from methanol through one-step catalysis method |
| CN104525057B (en) * | 2014-12-26 | 2017-06-06 | 太原理工大学 | A kind of synthesis gas two-step method prepares the device and technique of gasoline |
| CN105985793B (en) * | 2015-01-28 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of method that oxygen containing feed is transformed into gasoline |
| CN106146235B (en) * | 2015-05-15 | 2019-06-18 | 内蒙古丰汇化工有限公司 | The method that hydrocarbon products is prepared by methanol by one-step method |
| CN105001900B (en) * | 2015-07-31 | 2017-03-01 | 赛鼎工程有限公司 | A kind of technique through methanol synthesized gasoline for coke-stove gas |
| CN105154126B (en) * | 2015-07-31 | 2017-05-31 | 赛鼎工程有限公司 | Coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar method |
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