CN104693004B - Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths - Google Patents
Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths Download PDFInfo
- Publication number
- CN104693004B CN104693004B CN201310652737.7A CN201310652737A CN104693004B CN 104693004 B CN104693004 B CN 104693004B CN 201310652737 A CN201310652737 A CN 201310652737A CN 104693004 B CN104693004 B CN 104693004B
- Authority
- CN
- China
- Prior art keywords
- synthesis gas
- catalyst
- reaction
- mixed alcohol
- product
- 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.)
- Active
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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
-
- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the process of a kind of effective regulation synthesis gas mixed alcohol product carbon chain lengths, the reaction unit that the method uses is fixed-bed reactor, and this process includes: 1) catalyst tablet forming of mixed alcohol synthetic reaction will be used for after, broken, be filled in reaction tube；2) in hydrogen or synthesis gas atmosphere, also it is originally intended to the catalyst of mixed alcohol synthetic reaction, then, is cooled to 160 DEG C～180 DEG C；3) be passed through step 2) described in synthesis gas, and utilize step 2) catalyst that obtains, fixed-bed reactor carries out the reaction of synthesis gas mixed alcohol, obtains mixed alcohol product.The present invention can effectively control the low carbon product (C shorter to carbochain of synthesis gas mixed alcohol product1‑C5) or to the longer high-carbon product (C of carbochain5+) generate, it is achieved that the products distribution controllability of synthesis gas mixed alcohol, and on-the-spot on-line control can be realized.
Description
Technical field
The present invention relates to a kind of process regulating synthesis gas mixed alcohol product carbon chain lengths, particularly relate to one
Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths.
Background technology
The energy is to ensure that a national economy sustainable development and the essential condition of safety and stability.Day along with petroleum resources
Gradually exhausted, future source of energy structure will turn to based on coal and natural gas.The main energy sources resource of coal Ye Shi China, from resource
Rationally and effectively utilizing angle to consider, ICL for Indirect Coal Liquefaction is converted into liquid fuel and the correlational study of downstream chemical product, has non-
Often it is widely applied prospect.
It is C with the research that coal and natural gas are primary raw material Synthesis of mixed alcohols1One of important content of chemistry.Mixed alcohol
Application prospect is the brightest and the clearest.MAS refers to C1-C6Alcohol-based mixtures, be exactly a kind of excellent clean from the point of view of itself
Clean fuel.Secondly, low-carbon alcohols owing to octane number is high, calorific value antidetonation high, explosion-proof and gasoline compatibility is good, reduce burning after useless
The advantages such as the content of formaldehyde in gas, may be used for the fuel additives such as gasoline.MAS can be with isolated low-carbon alcohols
Class chemicals, and as the synthesis material of other chemical products.Consider from high added value angle, the economic worth of higher alcohols and should
More wide by prospect.Higher alcohols generally refer to 6 carbon atoms and above monohydric alcohol, are mainly used in synthesizing plasticizer, washing
Agent, surfactant and other fine chemicals.The method currently preparing higher alcohols has the following two kinds: by animal and plant oils and fats
Direct hydrogenation preparation and directly chemosynthesis, the former is limited to the supply of raw material, it is difficult to large-scale production, although the latter can advise
Mould produces, but is overly dependent upon oil product, there is also that flow process is longer simultaneously, technical sophistication, relatively costly and side reaction
The shortcoming such as more.It can be considered to directly prepared mixed alcohol especially higher alcohols by synthesis gas, this reaction scheme is short, and product is attached
Value added height, can be as one of alternative method preparing higher alcohols.
The most existing substantial amounts of by the report of preparing low-carbon mixed alcohol by synthetic gas, low carbon alcohol by synthetic gas has so far
Representational Catalytic processes and catalyst have four kinds:
(1) modified methanol synthetic catalyst (Cu/ZnO/Al2O3, ZnO/Cr2O3): this catalyst is by methanol synthesis catalyst
Add appropriate alkali metal or Modified With Alkali-earth Compounds and obtain (EP0034338A2, US4513100).On this type of catalyst
In product, methanol content is higher, but shortcoming to be Catalytic processes harsher.
(2) IFP (IFP) developed in the first Cu-Co and is co-precipitated low-carbon alcohol catalyst, has patent
US4122110,4291126 and GB2118061,2158730, this catalyst synthesis product be mainly C1-C6Straight chain n-alkanol,
By-product is mainly C1-C6Aliphatic hydrocarbon, reaction condition is gentle (similar to low pressure methanol synthesis catalyst), but less stable.
(3) molybdenum system sulfide catalyst (patent US4882360) of U.S. DOW company exploitation, this catalyst system is not only
Having resistance to SO_2, product water content is few, and higher alcohol content is higher, reaches 30～70%, the most mainly ethanol and positive third
Alcohol.The subject matter that this type of catalyst exists is that wherein auxiliary element easily and forms carbonyl compound between carbon monoxide, makes
Become the loss of auxiliary element, affect activity and the selectivity of catalyst, cause catalyst stability and life-span to be restricted.
(4) noble metal Rh base catalyst (such as US4014913 and 4096164): add to two in support type Rh catalyst
After planting transition metal or metal oxide auxiliary agent, having higher activity and selectivity to higher alcohols synthesis, special city is to C2 +Alcohol
Selectivity is higher, and product is based on ethanol.But Rh compound is expensive, catalyst is easily by CO2Poison, its activity and selectivity
Typically up to less than industrial requirement.
At present, relative synthesis gas directly prepares low-carbon alcohols, and synthesis gas is directly prepared the catalyst of higher alcohols both at home and abroad
Study the most relatively fewer.Domestic patent CN101310856B was once reported with activated carbon as carrier, the Co synthesis as active component is high
Catalyst of carbon alcohol and preparation method thereof, can one-step synthesis C2-C18Straight chain higher alcohol.United States Patent (USP) US4504600 reports one
Plant the ferrum-based catalyst of thallium auxiliary agent, hydrocarbon product can obtain C6-C12Higher alcohols.European patent EP 1017657B1 reports profit
CuCoMn and CuCoMg catalyst is prepared, containing C in alcohol product by the sedimentation method5-C11Higher alcohols.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of effective regulation synthesis gas mixed alcohol product carbon chain lengths
Process.By change technological parameter can effectively control synthesis gas mixed alcohol product to MAS, lower alkanes
Hydrocarbon or to high-carbon mixed alcohol, High-carbon alkane generate, it is achieved that the products distribution controllability of synthesis gas mixed alcohol.
For solving above-mentioned technical problem, the technique side effectively regulating synthesis gas mixed alcohol product carbon chain lengths of the present invention
Method, wherein, the reaction unit that this employing process uses is fixed-bed reactor, and this process includes following step
Rapid:
1) after the catalyst tablet forming of mixed alcohol synthetic reaction being used for, broken, it is filled in reaction tube；
2) in hydrogen or synthesis gas atmosphere, also it is originally intended to the catalyst of mixed alcohol synthetic reaction, then, is cooled to 160
DEG C～180 DEG C；
Wherein, synthesis gas is by H2, CO and CO2Constitute mixed gas or by H2The mixed gas constituted with CO；
3) be passed through step 2) described in synthesis gas, and utilize step 2) catalyst that obtains, in fixed-bed reactor
Carry out the reaction of synthesis gas mixed alcohol, obtain mixed alcohol product.
In described step 1), catalyst includes: CuFe base modification FT catalyst；This CuFe base modification FT catalyst includes:
Described in catalyst described in Chinese patent application CN101327435A or Chinese patent application CN101185899A
Catalyst；
Wherein, the weight percentage composition of described in Chinese patent application CN101327435A catalyst is: Cu:
20-60%, Fe:15-60%, Mn:0.4-20%, Zn:0.4-30%, MA: 0-5%；Wherein, MAIt is alkali metal, alkaline-earth metal or your gold
One or more in genus；
The weight percentage composition of catalyst described in Chinese patent application CN101185899A is: Cu:20-60%,
Fe:20-60%, Mn:0-30%, Zn:0-30%.
In described step 1), broken degree is for being crushed to 40～60 mesh；The consumption loaded is: catalyst and quartz sand with
Volume ratio is 1:1～after 1:1.5 mixing, filling.
Described step 2) in, the condition of reduction is: described catalyst in hydrogen or synthesis gas atmosphere with 1 DEG C/min～2
DEG C/min ramp to 200～600 DEG C, preferably 250～400 DEG C；Reduction air speed is 15000～20000h-1, reduce (activation)
Time is 0.5～24h, preferably 6～12h；
Described step 2), 3) in, the H in synthesis gas2/ (CO+CO2) mol ratio be 0.5～5, preferably 2～4, commonly using is 2
～2.5；
CO in synthesis gas2Mol ratio=the x/1 of/CO, wherein, x≤0.03 or 0.03 ＜ x ＜ 2.
As 0.03 ＜ x ＜ 2, mixed alcohol product is with the shorter low carbon product (C of carbochain1-C5) it is main；When x≤0.03,
Also can get the high-carbon product (C that substantial amounts of carbochain is longer5+), and realize low carbon product and high-carbon product on-line conversion tune in situ
Joint.
It addition, described synthesis gas includes: fresh synthesis gas, reaction cycle tail gas or the mixture of both.
In described step 3), the condition of the reaction carrying out synthesis gas mixed alcohol is: reaction temperature is 150～350 DEG C, excellent
Select 200～300 DEG C；Reaction velocity is 1000～20000h-1, preferably 4000～6000h-1；Operating pressure is 0.1～15MPa,
Preferably 2～6MPa, particularly preferred 6MPa.
The present invention by change technological parameter can effectively control synthesis gas mixed alcohol product to shorter low of carbochain
Carbon product (C1-C5) or to the longer high-carbon product (C of carbochain5+) generate, it is achieved that the products distribution of synthesis gas mixed alcohol can
Control property, it is possible to realize on-the-spot on-line control.Therefore, the present invention compared with prior art has a characteristic that
(1) distribution of mixed alcohol product can be controlled by regulation technique, can produce according to actual market demand low
Carbon alcohol or higher alcohols, motility is strong, can well adapt to the most fast changing economic market demand.
(2) in this technique, unstripped gas can be containing appropriate CO2, thus can save in gas making or CO in circulation of tail gas2's
Removing, reduces operating cost, it is easier to industrialization.
Detailed description of the invention
Preparing catalyst according to Chinese patent application CN101327435A preparation method, evaluating catalyst is in 5ml fixed bed
Reactor reacts.Stainless steel reaction pipe is internal diameter 11mm, and gas flowmeter uses BROOKS effusion meter, and through online
Correction obtains curve rear and enters practical operation.Catalyst is after online reduction, with N2By reactor pressure back pressure to 6.0MPa,
Then it is down to 180 DEG C, uses synthesis gas instead and gradually displace the N in reactor2, after about 24h after emptying, start mixed alcohol processed anti-
Should, synthesis gas enters reactor, the product products such as hot trap separation wax phase and oil phase, cold-trap after mass flowmenter measures
(0 DEG C to-3 DEG C) is by synthetic product and tail gas separation.
In order to ensure the accuracy of data, can start after catalyst 24h to be run to analyze, and sampling interval duration every time
It is greater than 18h, it is ensured that gathered sample products is representative.Product analysis uses Shimadzu and domestic China to like that chromatograph is divided
Analysis.H2、CO、CH4、CO2Respectively with two TCD detector (Ar and N2Doing carrier gas, chromatographic column is TDX-1) detection, with CO associate into
Row normalizing calculates.Alkane alkene uses fid detector detection, liquid phase H2O and CH3The product TCD(chromatographic columns such as OH are PorapakQ)
Detector and FID(chromatographic column are PorapakQ) detection, oil-phase product FID(chromatographic column HP-1 post, N2For carrier gas) detector
Detection, solid wax phase product CS2Being MXT-1 by FID(chromatographic column after dissolution process at 80 DEG C, carrier gas is N2) detector inspection
Survey.The mass balance of all assay products, C balance and O balance are held between 95%-105%.
Embodiment 1
The catalyst for mixed alcohol synthetic reaction (i.e. synthol catalyst) in the present embodiment is according to Chinese patent Shen
Please prepare by CN101327435A, each weight metal percentage composition in gained catalyst is as follows:
Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.
Reaction unit in the present embodiment is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, fill in reaction tube.Loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is H2, reduction air speed is 15000h-1, reduce after 250 DEG C with 1.2 DEG C/min ramp,
Recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure to 6.0MPa, then it is down to 180 DEG C, uses conjunction instead
Gas is become gradually to displace the N in reactor2, after about 24h after emptying, start reaction.Reaction condition is: the H in synthesis gas2/ (CO+
CO2) mol ratio=2.04, CO2Mol ratio x=0.025 of/CO, reaction temperature is 200 DEG C, and reaction velocity is 6000h-1, work
Pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 2
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.
Reaction unit in the present embodiment is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 2.25ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 16000h-1, with 1.5 DEG C/min speed
Rate is reduced after being warming up to 250 DEG C, and the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 180 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: the H in synthesis gas2/ (CO+CO2) mol ratio=1.86, CO2Mol ratio x=1.45 of/CO, reaction temperature is
200 DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 3
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.8ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 17000h-1, with 1.6 DEG C/min speed
Rate is reduced after being warming up to 300 DEG C, and the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 160 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: the H in synthesis gas2/ (CO+CO2) mol ratio=1.86, CO2Mol ratio x=0.015 of/CO, reaction temperature is
230 DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 4
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 2.1ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 18000h-1, with 1.8 DEG C/min speed
Rate is reduced after being warming up to 300 DEG C, and the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 180 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: the H in synthesis gas2/ (CO+CO2) mol ratio=2.04, CO2Mol ratio x=0.56 of/CO, reaction temperature is
250 DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 5
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 20000h-1, with 1 DEG C/min speed
Reducing after being warming up to 300 DEG C, the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 160 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: synthesis gas H2/ (CO+CO2) mol ratio=1.02, CO2Mol ratio x=1.05 of/CO, reaction temperature is 200
DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 6
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 20000h-1, with 1 DEG C/min speed
Reducing after being warming up to 300 DEG C, the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 180 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: the H in synthesis gas2/ (CO+CO2) mol ratio=4.04, CO2Mol ratio x=0.015 of/CO, reaction temperature is
230 DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 7
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 20000h-1, with 1 DEG C/min speed
Reducing after being warming up to 350 DEG C, the recovery time is 6h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 180 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: the H in synthesis gas2/ (CO+CO2) mol ratio=2.04, CO2Mol ratio x=0 of/CO, reaction temperature is 300
DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 8
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas, and reduction air speed is 20000h-1, carry out also after 300 DEG C with 1 DEG C/min ramp
Former, the recovery time is 12h.After reduction process terminates, with N2By reactor pressure back pressure to 6.0MPa, then it is down to 180 DEG C, changes
The N in reactor is gradually displaced with synthesis gas2, after about 24h after emptying, start reaction.Reaction condition is: the H in synthesis gas2/
(CO+CO2) mol ratio=1.86, CO2Mol ratio x=0.015 of/CO, reaction temperature is 250 DEG C, and reaction velocity is 4000h-1,
Operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 9
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN1011185899A, gained catalyst
Each weight metal percentage composition Cu:35.39%, Fe:31.10%, Mn:15.30%, Zn:18.21%.
Reaction unit in the present embodiment is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 20000h-1, with 1 DEG C/min speed
Reducing after being warming up to 300 DEG C, the recovery time is 12h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, is then down to 180 DEG C, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, start reaction.
Reaction condition is: synthesis gas H2/ (CO+CO2) mol ratio=2.04, CO2Mol ratio x=0.56 of/CO, reaction temperature is 250
DEG C, reaction velocity is 6000h-1, operating pressure is 6.0MPa, and reaction result is shown in Table 1, table 2.
Embodiment 10
Synthol catalyst in the present embodiment is prepared according to Chinese patent application CN101327435A, and gained catalyst is each
Weight metal percentage composition Cu:33.77%, Fe:43.21%, Mn:14.20%, Zn:6.76%, K:2.06%.Anti-in the present embodiment
Answering device is fixed bed reactors.
By catalyst tabletting and be crushed to 40-60 mesh, filling in reaction tube, loadings is 1.5ml, with 1.5ml microlith
Sand dilutes, and reducing atmosphere is synthesis gas (H2、CO、CO2Mixture), reduction air speed is 20000h-1, with 2 DEG C/min speed
Reducing after being warming up to 300 DEG C, the recovery time is 12h.After reduction process terminates, with N2By reactor pressure back pressure extremely
6.0MPa, after then rising to target temperature point, uses synthesis gas instead and gradually displaces the N in reactor2, after about 24h after emptying, open
Begin to react.Reaction condition is: reaction temperature is 250 DEG C, and reaction velocity is 6000h-1, operating pressure is 6.0MPa, in synthesis gas
H2/ (CO+CO2) mol ratio=1.86, CO2Mol ratio x=0.56 of/CO, reacting balance take at 3 after in situ switching and merging again
Gas, the H in synthesis gas2/ (CO+CO2) mol ratio=1.86, CO2Mol ratio x=0.015 of/CO, same reacting balance takes 3 points,
Its evaluation result data take 3 meansigma methodss, and reaction result is shown in Table 3, table 4.
From the evaluation result of embodiment 1-9 it can be seen that as CO synthesis gas2The mol ratio of/CO is 0.03 ＜ x ＜ 2
Time, although alcohol selectivity uprises in product, but major part is the low-carbon alcohols such as methanol, ethanol in terms of products distribution, and C6+(C6+It is
Refer to C6Above alcohol, the expression for conventional in low-carbon alcohols) alcohol almost without, this shows that mixed alcohol product is with low-carbon (LC) under this technique
Alcohol is main；When x≤0.03, C in terms of products distribution2+Alcohol selectivity substantially rises, and C6+Alcohol proportion increases, it is seen that
Mixed alcohol product is based on higher alcohols at the process conditions.
Find out from the evaluation result of embodiment 10, on same catalyst, product can be changed in situ by regulation technique
Thing is distributed, and is reversible from the results of view.
The catalyst reaction result of table 1 embodiment 1-9
The alcohol of table 2 embodiment 1-9, hydrocarbon product are distributed
The original position modulation synthetic gas catalyst reaction result of table 3 embodiment 10
Table 4 embodiment 10 modulation synthesis gas alcohol in situ, hydrocarbon product distribution
Claims (8)
1. the process regulating synthesis gas mixed alcohol product carbon chain lengths, it is characterised in that: described process is adopted
Reaction unit be fixed-bed reactor, and this process comprises the following steps:
1) after the catalyst tablet forming of mixed alcohol synthetic reaction being used for, broken, it is filled in reaction tube；
2) in hydrogen or synthesis gas atmosphere, be also originally intended to the catalyst of mixed alcohol synthetic reaction, then, be cooled to 160 DEG C～
180℃；
Wherein, synthesis gas is by H2, CO and CO2Constitute mixed gas or by H2The mixed gas constituted with CO；
3) be passed through step 2) described in synthesis gas, and utilize step 2) catalyst that obtains, carry out in fixed-bed reactor
The reaction of synthesis gas mixed alcohol, obtains mixed alcohol product；Described step 1) in, catalyst includes: CuFe base modification FT is catalyzed
Agent；Described CuFe base modification FT catalyst includes: catalyst described in Chinese patent application CN101327435A or China
Catalyst described in patent application CN101185899A；
Wherein, the weight percentage composition of described in Chinese patent application CN101327435A catalyst is: Cu:20-
60%, Fe:15-60%, Mn:0.4-20%, Zn:0.4-30%, MA: 0-5%；MAIt is in alkali metal, alkaline-earth metal or noble metal
One or more；
The weight percentage composition of catalyst described in Chinese patent application CN101185899A is: Cu:20-60%, Fe:
20-60%, Mn:0-30%, Zn:0-30%；
Described step 2), 3) in, the H in synthesis gas2/(CO+CO2) mol ratio be 0.5～5；CO in synthesis gas2/ CO rubs
You are ratio=x/1, wherein, and x≤0.03 or 0.03 ＜ x ＜ 2.
2. the method for claim 1, it is characterised in that: described step 1) in, broken degree is for being crushed to 40～60
Mesh；
The consumption loaded is: catalyst and quartz sand, with volume ratio as 1:1～after 1:1.5 mixes, load.
3. the method for claim 1, it is characterised in that: described step 2) in, the condition of reduction is:
Described catalyst in hydrogen or synthesis gas atmosphere with 1 DEG C/min～2 DEG C/min ramp to 200～600 DEG C；Reduction
Air speed is 15000～20000h-1, the recovery time is 0.5～24h.
4. method as claimed in claim 3, it is characterised in that: described step 2) in, described catalyst is at hydrogen or synthesis gas
With 1 DEG C/min～2 DEG C/min ramp to 250～400 DEG C in atmosphere；
Recovery time is 6～12h.
5. the method for claim 1, it is characterised in that: step 2), 3) in,
Described synthesis gas includes: fresh synthesis gas, reaction cycle tail gas or the mixture of both.
6. method as claimed in claim 5, it is characterised in that: the H in described synthesis gas2/(CO+CO2) mol ratio be 2～
4。
7. the method for claim 1, it is characterised in that: described step 3) in, carry out the reaction of synthesis gas mixed alcohol
Condition be:
Reaction temperature is 150～350 DEG C；Reaction velocity is 1000～20000h-1；Operating pressure is 0.1～15MPa.
8. method as claimed in claim 7, it is characterised in that: described reaction temperature is 200～300 DEG C；Reaction velocity is
4000～6000h-1；Operating pressure is 2～6MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652737.7A CN104693004B (en) | 2013-12-05 | 2013-12-05 | Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310652737.7A CN104693004B (en) | 2013-12-05 | 2013-12-05 | Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104693004A CN104693004A (en) | 2015-06-10 |
| CN104693004B true CN104693004B (en) | 2016-12-07 |
Family
ID=53340603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310652737.7A Active CN104693004B (en) | 2013-12-05 | 2013-12-05 | Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104693004B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659742A (en) * | 1982-03-26 | 1987-04-21 | Institut Francais Du Petrol | Process for manufacturing a mixture of methanol and higher alcohols from synthesis gas |
| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
| CN101327435A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Iron-copper based catalyst for synthesizing low carbon mixed alcohol and production method and use |
| CN101733122A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing low-carbon mixed alcohol from carbon dioxide-containing synthesis gas, preparation method and application |
| CN102319575A (en) * | 2011-06-03 | 2012-01-18 | 中国科学院广州能源研究所 | Cu-Fe-based catalyst used in synthesis of higher alcohol with synthetic gas, preparation method thereof and application thereof to process for synthesizing higher alcohol with synthetic gas |
| CN102872881A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst |
-
2013
- 2013-12-05 CN CN201310652737.7A patent/CN104693004B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4659742A (en) * | 1982-03-26 | 1987-04-21 | Institut Francais Du Petrol | Process for manufacturing a mixture of methanol and higher alcohols from synthesis gas |
| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
| CN101327435A (en) * | 2008-07-30 | 2008-12-24 | 中国科学院山西煤炭化学研究所 | Iron-copper based catalyst for synthesizing low carbon mixed alcohol and production method and use |
| CN101733122A (en) * | 2009-12-07 | 2010-06-16 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing low-carbon mixed alcohol from carbon dioxide-containing synthesis gas, preparation method and application |
| CN102319575A (en) * | 2011-06-03 | 2012-01-18 | 中国科学院广州能源研究所 | Cu-Fe-based catalyst used in synthesis of higher alcohol with synthetic gas, preparation method thereof and application thereof to process for synthesizing higher alcohol with synthetic gas |
| CN102872881A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst used in process of synthesizing low carbon mixed alcohol and preparation method and application of catalyst |
Non-Patent Citations (5)
| Title |
|---|
| Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst;Yongwu Lu等;《Applied Catalysis A: General》;20120412;第429-430卷;第48-58页 * |
| CO hydrogenation to mixed alcohols over co-precipitated Cu–Fe catalysts;Minggui Lin等;《Catalysis Communications》;20080318;第9卷;第1869-1873页 * |
| Cu-Fe基催化剂在煤基合成气制低碳混合醇中的应用;苏艳敏等;《洁净煤技术》;20131024;第19卷(第5期);第68-73页 * |
| Plasma-assisted preparation of Fe–Cu bimetal catalyst for higher alcohols synthesis from carbon monoxide hydrogenation;Hui Zhang等;《fuel》;20100425;第89卷;第3127-3131页 * |
| 用于低碳混合醇合成的Fe/CuZnSi催化剂研究;宁文生等;《现代化工》;20131031;第33卷(第10期);第66-69页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104693004A (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ting et al. | Low-temperature hydrogenation of CO2 to methanol over heterogeneous TiO2-Supported Re catalysts | |
| Zhou et al. | Hydrodeoxygenation of microalgae oil to green diesel over Pt, Rh and presulfided NiMo catalysts | |
| CN103433046B (en) | For the synthesis of the copper cobalt-based compound oxide catalyst of gas mixed alcohol especially higher alcohols and method for making and application | |
| CN102229520B (en) | Method for preparing alcohol by acetic acid gas phase hydrogenation | |
| Soares et al. | Glycerol as a source for fuels and chemicals by low-temperature catalytic processing | |
| Jung et al. | Effect of copper surface area and acidic sites to intrinsic catalytic activity for dimethyl ether synthesis from biomass-derived syngas | |
| Li et al. | Higher alcohols from synthesis gas using carbon-supported doped molybdenum-based catalysts | |
| Christensen et al. | Coupling of Alcohols over Alkali‐Promoted Cobalt–Molybdenum Sulfide | |
| CN105218289B (en) | A kind of method that unrighted acid original position hydrogenation decarboxylation prepares long chain alkane | |
| CN102716749B (en) | Auxiliary agent-modified catalyst for CO-CO2 co-hydrogenation synthesis of methanol | |
| Onyestyák et al. | Improving the catalytic behavior of Ni/Al2O3 by indium in reduction of carboxylic acid to alcohol | |
| CN102649079A (en) | Method for converting synthetic gas into low-carbon alkene with ferro-manganese base catalyst | |
| Mao et al. | A mechanistic basis for the effects of Mn loading on C2+ oxygenates synthesis directly from syngas over Rh–MnOx/SiO2 catalysts | |
| CN103613483B (en) | A kind of layering loading catalyst prepares the application in low-carbon alcohol at synthetic gas | |
| AU2013408110A2 (en) | Method for use in production of ethanol and coproduction of methanol | |
| Gądek et al. | Production of Methanol and Dimethyl ether from biomass derived syngas–a comparison of the different synthesis pathways by means of flowsheet simulation | |
| CN108325548A (en) | A kind of molybdenum sulphide and preparation method thereof for low carbon alcohol by synthetic gas | |
| CN106518657B (en) | A method of acetic acid is prepared by methanol carbonyl | |
| CN102690170B (en) | Method for preparing ethanol by acetic acid gas phase hydrogenation | |
| CN102319575A (en) | Cu-Fe-based catalyst used in synthesis of higher alcohol with synthetic gas, preparation method thereof and application thereof to process for synthesizing higher alcohol with synthetic gas | |
| CN107486226A (en) | Catalyst, the preparation method and its usage of preparation of low carbon olefines by synthetic gas | |
| CN107008502B (en) | A method of by methanol, carbon dioxide and hydrogen synthesis of acetic acid | |
| Pan et al. | Direct alcohol synthesis using copper/cobalt catalysts | |
| CN102649081A (en) | Reducing method for preparation of ethylene glycol catalyst by oxalate through hydrogenation | |
| CN104693004B (en) | Effectively regulate the process of synthesis gas mixed alcohol product carbon chain lengths |
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 |